Karim Benzema maintained his impressive scoring run against Valencia and Toni Kroos was also on target as Real Madrid eased to a 2-0 win in Sunday's LaLiga clash.
French striker Benzema netted for the fifth league game running in this fixture to open the scoring at Estadio Alfredo Di Stefano and Kroos added a second before half-time.
Valencia won the reverse fixture 4-1 in November, with Carlos Soler scoring a hat-trick of penalties, but they offered little attacking threat in a one-sided game in the Spanish capital.
Ferland Mendy had a goal ruled out in a low-key second half as Madrid, who lost Dani Carvajal to an injury on his return to action, made it three league wins in a row to move back into second place.
Valencia were seeking a first league double over Madrid since 1967-68 but found themselves behind to Benzema's 12th-minute strike.
Kroos played the ball to Benzema towards the left and the striker cut inside before curling a 20-yard shot into the bottom-right corner.
Losing Carvajal to an injury was a blow for the hosts but they did not lose any fluency as Kroos fired in from the edge of the box for only his second goal this season.
Valencia, now without an away league win against Madrid in 13 attempts, pressed for an equaliser and called Thibaut Courtois into action through a Maxi Gomez drive.
Mendy had the ball in the net soon after, only for his celebrations to be cut short as VAR adjudged the defender's heel to be offside before he converted Vinicius Junior's pass.
Zinedine Zidane's men went close to adding to their tally, but Jaume Domenech denied Benzema at his near post and Mendy lost his footing when shooting from a good position late on.
'One game at a time', says calm Slot after Leverkusen thrashing
Arne Slot insisted he will continue to look at "one game at a time" after leading Liverpool to a 4-1 victory over Bayer Leverkusen in the Champions League on Tuesday.
Luis Diaz's second-half hat-trick along with Cody Gakpo's 63rd-minute strike spoiled Xabi Alonso's Anfield return, moving the Reds top of the 36-team standings.
Liverpool have now won all four of their Champions League games under Slot. It’s only the second time that they have won all four opening games in a single season.
The Reds are now top of both the Premier League and Champions League, though Slot was keen to focus on the next task, which comes in the shape of Aston Villa on Saturday.
"I don't know if it was that much to do with intensity, but we took more risk," Slot said.
"They overloaded the midfield a lot, and we adjusted at half-time and took the risk to play one v one all over. We had better chances in the first half and they weren't a goal threat.
"As much as this time, how good they are in Europe, sometimes a strong target man is better than someone a bit faster.
"Curtis Jones did an incredible pass, and then you have someone with the pace of Lucho to finish it off. The pass was as good as the goal, in my opinion.
"You don't look ahead as a manager in the next three months. You're always one game at a time. We've got Aston Villa on Saturday, another tough game."
Diaz's treble saw him become only the second Colombian player to score a hat-trick in the Champions League, after Faustino Asprilla for Newcastle against Barcelona in 1997.
And he insisted that things have started brightly for Slot at Anfield, but said his team-mates must continue to perform to have something to show for it at the end of the season.
"The most important thing is the three points in this edition of the Champions League so we can keep progressing in the competition," Diaz said.
"Things have gone so well with the new manager, it wasn't easy for him to come in and fill Jurgen Klopp's shoes.
"Hopefully, we'll have something to show for it at the end of the season.
"We have top-quality players all over the pitch and I really enjoyed playing in that position today. I'm just happy to be on the pitch.
"I need to go and find that ball now because I need to keep it somewhere special at home."
For Alonso and Leverkusen, meanwhile, it marked a first Champions League defeat since 2022, while also conceding four or more goals in an away match in the competition since 2013 against Manchester United.
"It's painful the result more than the performance, probably," Alonso told Amazon Prime.
"But this is the Champions League, this is the highest level, and today it wasn't enough for us."
"It's too early to tell, but I can see that Liverpool have a very good balance, a very complete team.
"They work with 11 players, and they have the power to hold a clean sheet, which is important in the Champions League.
"In the Premier League, let's see. It's early to tell but it's looking good."
Alonso, who won the Champions League with Liverpool in 2005, was serenaded by the home supporters at Anfield during the contest.
"I tried to separate the game and the pain from the result from the nice feelings to come back. I'm really happy and thankful for that reception," he added.
Bologna 0-1 Monaco: Kehrer maintains visitors' impressive Champions League start
Monaco defender Thilo Kehrer scored a late goal to earn a 1-0 Champions League victory for his side at Bologna on Tuesday.
Monaco captain Kehrer, left unmarked in front of goal four minutes from time, stretched out a leg to poke the ball home from a flicked-on corner to snatch the points.
The visitors maintained their unbeaten start to this season’s Champions League while also dealing Bologna their first-ever home defeat in European competition.
Both sides saw goals chalked off in the first half, Monaco's Wilfried Singo being penalised for a foul on Lukasz Skorupski before Santiago Castro saw a curling strike disallowed for a foul in the build-up.
The two Polish goakeepers, Monaco's Radoslaw Majecki and Bologna's Skorupski, both made several fine saves to keep the game goalless until Kehrer got the all-important touch on an inswinging corner late on.
The win puts Monaco in third place with 10 points, while Bologna are down in 30th spot with one point after four games.
Data Debrief: Long-awaited shutout for Monaco
Monaco have now won consecutive games in the Champions League for the first time since a run of three in 2017, also ending a 23-game run without a clean sheet in the competition.
Bologna, meanwhile, are the only side in this season's Champions League to play four matches and fail to score, despite registering 48 shots in total and an xG tally of 3.19.
Sheffield United go second after late turnaround, Plymouth continue good home form
Sheffield United staged a late turnaround to win 2-1 away to Bristol City and go second in the Championship, one point behind leaders Sunderland who play on Wednesday.
The game started slowly, with the hosts not opening the scoring until a 75th-minute Anis Mehmeti penalty after a foul on Sinclair Armstrong by goalkeeper Michael Cooper.
The Blades showed great character to haul themselves back into the game, with 18-year-old Ryan One scoring the equaliser in the 86th minute.
But things went up a notch in stoppage time when Robert Dickie was given a straight red card for a cynical foul on Callum O'Hare 35 yards out.
The drama wasn't finished yet and with seconds to go, Harrison Burrows smashed home a left-foot rocket to win the game for the Blades.
At the bottom of the table, Plymouth opened a four-point gap between themselves and the relegation zone with a 1-0 victory over bottom-of-the-table Portsmouth.
The victory means that Wayne Rooney's side have dropped just two points in their last five games at Home Park, having lost six on the bounce in all competitions away.
It is now four without a victory for Portsmouth, who have earned just nine points in their opening 14 matches back in the Championship.
Elsewhere, Middlesbrough responded to their 3-0 defeat at home to Coventry City last weekend by beating second-bottom Queens Park Rangers 4-1 on the road.
That was a first victory in three for Michael Carrick's side, who are one place below the play-off positions and trail only by goal difference.
QPR are four points behind fourth-bottom Preston North End, having failed to win any of their last 10 league games.
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