French side Toulouse claimed the biggest result of the night by defeating Premier League giants Liverpool 3-2 at home.
Despite Liverpool taking an early lead through an own goal, Toulouse roared back with strikes from Aron Dønnum and Thijs Dallinga either side of half-time.
“This is a historic night for the club,” Toulouse manager Philippe Montanier said. “To beat a team like Liverpool shows how far we have come.”
The visitors set up a grandstand finish when Diogo Jota pulled one back late on after Mohamed Salah came off the bench. But Toulouse held on for a famous victory.
Elsewhere, Brighton secured their first ever away win against Ajax, beating the Dutch giants 2-0 in Amsterdam.
Ansu Fati and Simon Adingra netted first-half goals to put Brighton in control. Ajax’s Brian Brobbey hit the post twice after the break but Brighton saw out the win.
“It’s a massive result for us at a historic stadium,” said Brighton boss Roberto De Zerbi. “The players followed the gameplan perfectly.”
Slavia Praha also pulled off an upset by defeating Roma 2-0 at home. Second-half goals from Václav Jurečka and Lukáš Masopust downed Jose Mourinho’s side.
“This is a very disappointing night for us,” Mourinho said. “We lacked creativity and Slavia fully deserved to win.”
In Group A, West Ham moved top with a 1-0 home victory over Olympiacos thanks to Lucas Paqueta’s second-half strike.
Rangers are also in pole position in Group C after beating Sparta Prague 2-1 at Ibrox through goals from Danilo Pereira and Todd Cantwell.
Pedro Goncalves netted two penalties as Sporting Lisbon defeated Rakow Czestochowa 2-1 despite having Bogdan Racovitan sent off early on.
Elsewhere, Borja Iglesias and Abdessamad Ezzalzouli netted braces as Real Betis thumped Aris Limassol 4-0 to remain top of Group C.
And Marseille moved clear at the summit of Group B with a 2-0 win away at AEK Athens after second-half goals from Chancel Mbemba and Ismaila Sarr.
With two matches left, more drama is in store as teams scramble to reach the Europa League knockout stage after a thrilling matchday 4.
Europa League Tickets
Matchday 5 fixtures
Freiburg vs Olympiacos – Buy Europa League Tickets
TSC vs West Ham – Buy Europa League Tickets
AEK Athens vs Brighton – Buy Europa League Tickets
Sparta Praha vs Real Betis – Buy Europa League Tickets
Atalanta vs Sporting CP – Buy Europa League Tickets
Marseille vs Ajax – Buy Europa League Tickets
Rangers vs Aris Limassol – Buy Europa League Tickets
Maccabi Haifa vs Rennes – Buy Europa League Tickets
Liverpool vs LASK – Buy Europa League Tickets
Villarreal vs Panathinaikos – Buy Europa League Tickets
Servette vs Roma – Buy Europa League Tickets
Häcken vs Leverkusen – Buy Europa League Tickets
Matchday 6 fixtures
Union SG vs Liverpool – Buy Europa League Tickets
LASK vs Toulouse – Buy Europa League Tickets
Rennes vs Villarreal – Buy Europa League Tickets
Roma vs Sheriff Tiraspol – Buy Europa League Tickets
Leverkusen vs Molde – Buy Europa League Tickets
West Ham vs Freiburg – Buy Europa League Tickets
Brighton vs Marseille – Buy Europa League Tickets
Real Betis vs Rangers – Buy Europa League Tickets
Raków Czestochowa vs Atalanta – Buy Europa League Tickets