Europa League finalists Rangers will have to negotiate past Royale Union Saint-Gilloise in the Champions League third qualifying round, where PSV meet Monaco.
Giovanni van Bronckhorst's side entered the qualifying stages through their second-place finish in last season's Scottish Premiership, where winners progress to the play-off stage and losers go automatically into the Europa League group stage.
Rangers also embarked on an impressive run to the Europa League final last season, getting past Borussia Dortmund, Braga and RB Leipzig before being defeated on penalties by Eintracht Frankfurt in Seville.
Union finished second in Belgium's First Division A after a 48-year top-flight absence and will pose a tough task in the two-legged clash, with the first meeting on August 2-3 before the return tie a week later.
Rangers lost at this round to Malmo last year and last made the group stage of UEFA's premier club competition back in 2010-11.
PSV were beaten Europa Conference League quarter-finalists last season, but the team now led by Ruud van Nistelrooy earned a shot at the Champions League after finishing second in the Eredivisie, and will face Monaco.
The Ligue 1 side seemed set to secure group-stage qualification themselves but will have to battle through qualification after they were pipped for second place on the final day of the season by Marseille.
In the other league path fixtures, the winner of Dynamo Kyiv and Fenerbahce will meet Austria's Sturm Graz, while last year's Champions League quarter-finalists Benfica will face either Midtjylland or AEK Larnaca.
The draw for the Champions League play-off round will be on August 1, with those ties taking place over August 16-17 and 23-24.
Girona have little to lose and everything to gain, says Michel
Girona have plenty to gain and little to lose when they visit PSV in the Champions League, coach Michel claimed.
Despite securing a maiden European triumph over Slovan Bratislava last month, Girona are still struggling to find their best form, dealing with a long list of players out injured.
Following a LaLiga win over Leganes on Saturday, Michel said his players may not be full of energy but have the mentality to look for points at the Philips Stadion.
A positive result could be vital, given Girona then take on the likes of Liverpool, Milan and Arsenal.
"We have a lot to win and little to lose," Michel said ahead of Girona's first ever meeting with PSV.
" We are playing against a historic team with European titles. We don't come with all the energy I want, but we do come with a mentality.
"We need the points and, of course, every game is important. I don't know how high the bar will be to get into the top (places) but we are on a privileged stage and we will compete."
Girona occupy the 24th and final play-off place in the 36-team Champions League table, with three points from three games. PSV are in 28th with two points.
"We have to try to be the ones who dominate and who have the ball. We have to try to make them look towards their goal, if we give them control it will be very difficult for us to keep up the pace and hold them off," Michel added.
"PSV have been practically unbeaten at home for two years in a row. They are a great team with tremendous pressure and pace.
"We know how difficult it will be and if we want to get anything out of them we have to match their intensity."
Spanish teams have lost all four of the away games they have played in the Champions League this season.
PSV, on the other hand, are unbeaten in their last five home matches in the UEFA Champions League; their longest run without a home defeat in the competition since December 2005 (11 games). However, four of the five games in their current run have ended in stalemates (W1), including each of the last three.
Neymar suffers fresh injury blow
Neymar sustained a new injury as he was forced off during Al-Hilal's AFC Champions League Elite win over Esteghlal.
Aleksandar Mitrovic plundered a hat-trick on Monday to seal a 3-0 win.
But Al-Hilal's victory was soured by an injury to Neymar, who had to make way just 29 minutes after he came on as a second-half substitute.
The Brazilian, who has just returned from over a year out of action following a serious knee injury, was forced off with what appeared to be a thigh issue.
Indeed, Monday's appearance was only the 32-year-old's second for Al-Hilal since his comeback.
He has featured just seven times for the Saudi Pro League champions in all competitions since his big-money move from Paris Saint-Germain in 2023.
PSV seek to bounce back from Ajax loss
PSV want to use Tuesday's Champions League clash against Girona as a chance to bounce back after losing their 100% record in domestic football.
They still lead the Eredivisie by 15 points but after winning 10 games on the trot, let a 2-1 lead slip and went down 3-2 to Ajax in Amsterdam on Saturday.
PSV have a good chance to get back on track when they host Girona in what will be the first meeting between the teams.
"Everyone who has played football has lost at some point," said PSV coach Peter Bosz on Monday.
"You go home with a bad feeling and wake up the next day with a bad feeling. But then you also know that the next match is coming up.
"When you play in Europe, there are two or three days in between. It is like that almost every week, so as a player or as a coach you have to learn to move on from your disappointment quickly. We discuss the game afterwards and then we draw a line under it and move on to the next one."
Girona have already taken on PSV's domestic rivals Feyenoord in the new-look Champions League this season, losing at the start of last month, though Bosz is expecting a stern test form last season's surprise package in LaLiga.
"A team that wants to dominate opponents," Bosz said of their Spanish opponents.
"Also against Feyenoord, more possession, 11 corners to Feyenoord's zero. They want to build from the back, play real football.
"They did a great job in Spain last year. If you finish third there, that's something very special. You need a lot of quality, otherwise you won't last a season. This year they're having a bit more trouble, also because of the extra matches in the Champions League."
PSV have yet to win in the group phase this season, while they have won just two out of 20 European Cup/Champions League games against Spanish teams (D9 L9).
However, the last Spanish side to win away at PSV in European competition was Granada in October 2020 in the Europa League (2-1), with each of the last three visiting sides failing to win there (D2 L1): Real Sociedad (D1) and Sevilla on two occasions (D1 L1).
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