Angel Di Maria hit a late winner for Real Madrid at Auxerre as the Spanish giants jumped to the top of Group G.
Madrid last won the Champions League in 2002 when Zinedine Zidane's famous volley secured victory over Bayer Leverkusen at Hampden Park, Glasgow.
They have invested heavily in a mission to reassert themselves in Europe and in the Primera Division, and their summer signing from Benfica came to their rescue in France, firing in well after fellow recent recruit Mesut Ozil found him with a cross to make the breakthrough after 81 minutes and clinch a 1-0 victory.
AC Milan, who beat Auxerre in their opening match, were held 1-1 in Holland by Ajax tonight.
Mounir El Hamdaoui put Ajax ahead after 23 minutes after smart work from Luis Suarez, but former Ajax hero Zlatan Ibrahimovic found a leveller for Milan 14 minutes later, after an assist from another one-time favourite of the home crowd, Clarence Seedorf.
Roma recovered from their opening defeat to Bayern Munich in Group E by beating CFR Cluj 2-1 tonight.
The goals did not come until after the midway point of the second half, with defender Philippe Mexes firing in a crisp shot for the opener after 69 minutes and Marco Borriello striking a superb volleyed second two minutes later.
Cluj replied seven minutes later when Ionut Rada headed in, but they could not find an equaliser.
Bayern came from behind to win 2-1 at Basle, who led from the 17th minute thanks to Alexander Frei's elegant curling strike. Bayern levelled with a penalty from Bastian Schweinsteiger in the 56th minute, after Thomas Muller was impeded by Benjamin Huggel, and Schweinsteiger struck again with a minute remaining to pinch the points.
Chelsea were too strong for Marseille in their Group F clash at Stamford Bridge, doing the damage early in a 2-0 victory.
John Terry put the Premier League champions ahead after seven minutes and Nicolas Anelka fired home a penalty after 28 minutes.
Spartak Moscow joined Chelsea on six points from two games with a 3-0 home win over MSK Zilina, Ari scoring twice before Ibson added the third.
Arsenal and Shakhtar Donetsk look set to dominate Group H after both eased to the six-point mark tonight.
Shakhtar swept Braga aside 3-0, with Luiz Adriano scoring twice in the second half before Douglas Costa, whose passes had set up the opening two goals, added the finishing touch with a stoppage-time penalty.
Arsenal followed up their 6-0 thrashing of Braga in the first round of games by winning 3-1 away to Partizan Belgrade.
Andrei Arshavin drilled in Arsenal's opening goal after 15 minutes but Cleo's penalty made it level at the interval.
Marko Jovanovic was dismissed for a professional foul on Marouane Chamakh in the 56th minute, but Arshavin missed the penalty which followed.
However Chamakh made sure the penalty miss would not prove costly by restoring Arsenal's lead after 71 minutes, and with eight minutes remaining Sebastien Squillaci headed his first goal for the London club.