Real Madrid coach Jose Mourinho presided over the nine-time champions' triumph against Ajax in the same Santiago Bernabeu stadium where he won last season's final with Inter Milan.
"We pressed a lot and we didn't let Ajax play how they like to play," Mourinho said. "My forwards just weren't sharp in front of goal."
Milan, Madrid's biggest rival in Group G, beat Auxerre after two goals from new signing Zlatan Ibrahimovic.
Cesc Fabregas and Carlos Vela each scored twice in Arsenal's 6-0 rout of Portuguese side Braga, while Nicolas Anelka's double helped Chelsea surge to a 4-1 victory over newcomer Zilina.
Bayern Munich, beaten by Inter in the final in May, defeated AS Roma 2-0 in Group E.
In the Spanish capital, Madrid went ahead in the 31st minute when midfielder Xabi Alonso's corner was deflected in by Ajax defender Vurnon Anita.
The second goal took until the 73rd to arrive, with striker Gonzalo Higuain well placed at the far post to score from Mesut Oezil's cross.
"It looked like boys against men tonight," Ajax coach Martin Jol said. "They clearly dominated the game."
In the other group match, Ibrahimovic broke the deadlock in the 66th after linking up with Kevin-Prince Boateng and Ronaldinho.
The Sweden striker's second came three minutes later, completing a slick counter-attacking move that began with Robinho carrying the ball from defense before Ronaldinho's deft pass reached Ibrahimovic.
"Ibra had a good game tonight," Milan coach Massimo Allegri said. "He is a very important player for us - for his technique and the way he leads the attack."
Chelsea maintained their superb start to the season, having opened their Premier League title defence with four wins, with an emphatic win in Group F despite the absence of suspended striker Didier Drogba.
The visitors raced into a 3-0 lead inside 30 minutes against tournament newcomer Zilina. Anelka's cross was turned in by Michael Essien before the French striker hit two goals himself.
Soon after, Chelsea goalkeeper Petr Cech almost gifted the home side an equaliser, fumbling Robert Jez's free kick before recovering to stop the ball going into the net.
Daniel Sturridge hit Chelsea's fourth in the 48th after latching onto Yossi Benayoun's through ball.
Zilina's consolation goal came in the 55th when an unmarked Tomas Oravec pounced on the loose ball from Branislav Ivanovic's deflection after Cech had failed to hold on to a cross.
In the other Group F match, defender Cesar Azpilicueta scored a late own-goal to give Spartak Moscow a 1-0 win at Marseille, which wasted several scoring chances.
In the Spanish capital, Madrid went ahead in the 31st minute when midfielder Xabi Alonso's corner was deflected in by Ajax defender Vurnon Anita.
The second goal took until the 73rd to arrive, with striker Gonzalo Higuain well placed at the far post to score from Mesut Oezil's cross.
"It looked like boys against men tonight," Ajax coach Martin Jol said. "They clearly dominated the game."
In the other group match, Ibrahimovic broke the deadlock in the 66th after linking up with Kevin-Prince Boateng and Ronaldinho.
The Sweden striker's second came three minutes later, completing a slick counter-attacking move that began with Robinho carrying the ball from defense before Ronaldinho's deft pass reached Ibrahimovic.
"Ibra had a good game tonight," Milan coach Massimo Allegri said. "He is a very important player for us - for his technique and the way he leads the attack."
Chelsea maintained their superb start to the season, having opened their Premier League title defence with four wins, with an emphatic win in Group F despite the absence of suspended striker Didier Drogba.
The visitors raced into a 3-0 lead inside 30 minutes against tournament newcomer Zilina. Anelka's cross was turned in by Michael Essien before the French striker hit two goals himself.
Soon after, Chelsea goalkeeper Petr Cech almost gifted the home side an equaliser, fumbling Robert Jez's free kick before recovering to stop the ball going into the net.
Daniel Sturridge hit Chelsea's fourth in the 48th after latching onto Yossi Benayoun's through ball.
Zilina's consolation goal came in the 55th when an unmarked Tomas Oravec pounced on the loose ball from Branislav Ivanovic's deflection after Cech had failed to hold on to a cross.
In the other Group F match, defender Cesar Azpilicueta scored a late own-goal to give Spartak Moscow a 1-0 win at Marseille, which wasted several scoring chances.
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