Chelsea moved up to fifth in the league phase standings following a statement 3-0 win against Barcelona, Borussia Dortmund joining the Blues on ten points courtesy of a 4-0 victory at home to Villarreal.
Manchester City remain similarly well placed despite missing the chance to go top of the table having suffered a 2-0 home loss to Leverkusen. We round up all the action from the opening night of UEFA Champions League Matchday 5.
Simulate the league phase
Chelsea 3-0 Barcelona
Estêvão scored for a third successive league phase match and Liam Delap opened his European account as Chelsea cruised to victory.
After visiting forward Ferran Torres struck a fine early chance wide, Barça's Jules Koundé inadvertently turned in Pedro Neto's shot for the 27th-minute opener.
Ronald Araújo received a second caution for the Spanish side in the 44th minute, followed by Estêvão's thrilling run and strike ten minutes after half-time and Delap's finish from Enzo Fernández's pass with 17 minutes remaining.
Player of the Match: Marc Cucerella (Chelsea)
Manchester City 0-2 Leverkusen
The Werkself ended Man City's unbeaten league phase start thanks to Alejandro Grimaldo's well-taken strike and Patrik Schick's glancing header. City almost claimed the opener early on, but Nathan Aké forced a fine reaction stop from Mark Flekken.
The visitors weathered the early pressure, and midway through the first half captain Grimaldo applied the finish to a well-worked Leverkusen counter.
The Bundesliga outfit were indebted to Flekken's reactions on a number of occasions and doubled their advantage soon after the interval when Schick nodded in deftly from Ibrahim Maza's curling cross to end City's 23-match, seven-year unbeaten home run in the group stage/league phase.
Player of the Match: Mark Flekken (Leverkusen)
B. Dortmund 4-0 Villarreal
Serhou Guirassy took his Champions League tally to 18 goals in 23 games – a total bettered only by Erling Haaland – as Borussia Dortmund eased to victory against winless Villarreal.
Guirassy headed in on the line seconds before half-time then added a second from a penalty rebound after Juan Foyth was sent off for handball on the line. Karim Adeyemi's effort and a Daniel Svensson header clinched victory, with another missed spot kick in between from substitute Fábio Silva.
Player of the Match: Serhou Guirassy (Dortmund)
Galatasaray 0-1 Union SG
Promise David's deft finish helped Union SG claim their first league phase victory since Matchday 1, ending Galatasaray's three-match winning run in the process. The visitors got the breakthrough just before the hour when David steered in Adem Zorgane's precise cutback.
The hosts, deprived of the services of six-goal forward Victor Osimhen due to injury, had struck the post approaching the half-hour mark via Gabriel Sara's fierce strike. Davinson Sánchez came closest to levelling with 15 minutes left but could only scoop over from close range. The hosts' Arda Ünyay was dismissed late on.
Player of the Match: Adem Zorgane (Union SG)
Marseille 2-1 Newcastle
Pierre-Emerick Aubameyang scored twice in the first five minutes of the second half to complete a rousing turnaround against Newcastle.
The visitors led inside six minutes when Harvey Barnes put away a cross from the right, but it was the French hosts who looked the most threatening thereafter. Aubameyang had multiple efforts before the break but made no mistake after the interval with two clinical finishes.
Player of the Match: Pierre-Emerick Aubameyang (Marseille)
Ajax 0-2 Benfica
Samuel Dahl and Leandro Barreiro's emphatic finishes from inside the box earned Benfica their first points. Dahl lashed in the sixth-minute opener after Vitězslav Jaroš brilliantly stopped Richard Ríos' header, although the Portuguese side then needed Anatoliy Trubin to push behind shots from Davy Klaassen and competition debutant Rayane Bounida.
Klaassen rolled a presentable chance wide before Barreiro exchanged passes with Fredrik Aursnes during added time and blasted in, ensuring the Eagles prevailed and Ajax suffered a fifth defeat.
Player of the Match: Samuel Dahl (Benfica)
Napoli 2-0 Qarabağ
Scott McTominay was involved in both goals as Napoli earned their second win of the league phase. The first half finished goalless despite spectacular attempts at both ends – Qarabağ forward Emmanuel Addai sending a long-range shot just wide before a David Neres overhead kick was palmed away by Mateusz Kochalski.
Kochalski also denied Rasmus Højlund from the penalty spot, but was beaten after the hour when McTominay nodded in. The hosts doubled their lead seven minutes later as Mathías Olivera's cross found McTominay, whose hooked volley was inadvertently touched in by Marko Janković.
Player of the Match: Scott McTominay (Napoli)
Bodø/Glimt 2-3 Juventus
Juventus produced a superb finish to come from behind and win in Norway. The hosts had the better of the opening 45 minutes and took the lead when Ole Didrik Blomberg slammed in after a corner had been helped on.
But Loïs Openda was well placed to swivel and score before Weston McKennie's header put Juve ahead. Sondre Brunstad Fet's 87th-minute penalty looked to have given the home side a point only for Jonathan David to fire in the winner a minute into added time.
Player of the Match: Kenan Yıldız (Juventus)
Slavia Praha 0-0 Athletic Club
Jindřich Staněk produced a decisive display for Slavia Praha as they played out a goalless draw with Athletic Club which both sides will have been disappointed not to win.
Oihan Sancet had the best chance of the first half as Athletic hit Slavia on the counterattack, Staněk reacting sharply to repel the chance.
The Spanish side started quickly in the second 45 and Staněk pulled off three vital stops in short succession, all from Robert Navarro. Slavia's best chance came from Štěpán Chaloupek but his close-range effort was poked high over the bar.
Player of the Match: Aitor Paredes (Athletic)