Athletic Bilbao avenged their Supercopa de Espana final loss by defeating Real Madrid 1-0 in Thursday's Copa del Rey quarter-final.
Alex Berenguer struck a brilliant winner in the 89th minute to send Marcelino's men into the last four, where Valencia, Real Betis and Rayo Vallecano await.
Madrid had beaten Athletic 2-0 in last month's Supercopa final but could not find a breakthrough at San Mames in the absence of Karim Benzema.
It means Athletic, who eliminated Barcelona in the previous round, could now reach their third consecutive Copa final, having lost the previous two to Barca and Real Sociedad.
Clear-cut chances were scarce in the first half, but it was Athletic who carried the threat, with 10 shots to Madrid's three despite having only 41.3 per cent of the possession.
Indeed, Carlo Ancelotti's men ended the half with just 0.1 expected goals, their lowest tally for the first 45 minutes of any match since a 1-0 away win over Real Valladolid in January 2020.
Inigo Martinez saw a header well saved by Thibaut Courtois early in the second half, before Raul Garcia glanced an effort wide via a deflection and Berenguer, on for the injured Nico Williams, fired over.
Madrid began to assume more control as the 90 minutes wore on and Casemiro spurned a great chance, firing straight at Julen Agirrezabala from Marco Asensio's clever backheel.
Yet just as extra time beckoned, Berenguer produced a moment of magic, turning cleverly onto his left foot inside the Madrid box before bending a superb strike to the right of Courtois.
Barcelona must 'work hard' to achieve Champions League glory, says Flick
Hansi Flick tempered expectations of Barcelona's chances of silverware in his first season in charge ahead of facing Red Star Belgrade in the Champions League.
Flick has led Barca to 13 wins from 15 games in all competitions, scoring 50 goals in those games while conceding just 14 times.
Some standout matches have seen Barca thrash Clasico rivals Real Madrid 4-0 while also brushing aside Bayern Munich 4-1 in the Champions League in their last match in the competition.
While Flick understood the fans' excitement after those results, he urged his side to keep their feet on the ground with a long season still in front of them.
"We have to work hard. There are many teams who dream of the same thing, of winning (the Champions League)," Flick said.
"For the moment, we're going to focus on working hard and grinding out, so then we'll see what happens. We have to focus on our goal which is to keep improving.
"A team's form fluctuates a lot over a long season. The important thing is to focus on winning the next match. Sure, after the match against Bayern everything changed.
"But we are just starting. The important thing is how we finish the season. We could say that our goal is to be in the top eight."
Flick, however, insisted he was not surprised by his side's impressive start to the campaign despite enduring a trophyless season last term.
Barca are nine points clear at the top of LaLiga and 11th in the Champions League table ahead of facing Red Star, who are without a win from their three games so far.
"Before we came here we analysed the whole team, every player. We realised that there was very good quality overall," Flick said.
"Another thing to point out is that we wanted to improve how we defend and did small changes in the way we play. The players liked it and they are happy working on it.
"The players play a big role, they are helping us a lot.
"The start was already good on the pre-season in North American and the players are very happy, although there are still many things to improve."
And Barca will be confident of keeping their fine form going against a side that has lost 81% of their matches in the Champions League (P21 W2 D2 L17).
This is the first European meeting between the two sides since October 1996 in the Cup Winners’ Cup, a 1-1 draw with Giovanni cancelling out a Zoran Jovicic's opener for the Serbians.
PSV 4-0 Girona: Dutch side get first win of Champions League
PSV Eindhoven won their first match in the Champions League this season as they thrashed Girona 4-0 at the Philips Stadion on Tuesday.
Ryan Flamingo got the scoring under way after 16 minutes as he turned Malik Tillman's long throw home, despite replays showing that it should have been disallowed as Tillman's foot was over the byline before releasing the ball.
Tillman got himself on the scoresheet 17 minutes later with a fine finish after he arribed into the box unopposed.
Things went from bad to worth for Girona after half-time, with Arnau Martinez receiving a red card 10 minutes into the second half for a second bookable offence.
From then, it was all one-way traffic and PSV might feel aggrieved not to have won by a bigger margin given their glut of second-half chances.
Ismael Saibari was next to put the ball in the back of the net, although his effort was ruled out for a foul in the build-up following a VAR review.
Johan Bakayoko did get PSV's third with seven minutes to go, before a Ladislav Krejci own goal wrapped up the rout in the 88th minute. The result leaves Girona 26th in the table on three points, while PSV are 19th with five points.
Odegaard returns to full Arsenal training ahead of Inter tie
Arsenal captain Martin Odegaard has returned to full training after spending two months out of action with an ankle injury.
Odegaard has missed 12 matches for the Gunners in all competitions after damaging his ankle ligaments against Austria while on international duty with Norway in September.
The 25-year-old midfielder trained with Arsenal ahead of their trip to the San Siro to face Inter in the Champions League on Wednesday.
Mikel Arteta's side have, however, struggled in Odegaard's absence recently, failing to win any of their last three games in the Premier League.
In the seven games that Odegaard has missed in the top-flight, Arsenal's win percentage dropped from 66.7% to 42.9% after going unbeaten in their first three games.
The Gunners have also averaged 1.6 points per game without Odegaard, compared to 2.3 points won with the Norwegian in their ranks.
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