Borussia Dortmund beat Real Madrid 2-1 to go top of Group D ahead of Jose Mourinho's men.
Robert Lewandowski netted a 36th-minute opener for the Germans and, although Cristiano Ronaldo cancelled it out within two minutes, Marcel Schmelzer hit the home side's winner in the 64th minute.
Real coach Jose Mourinho remarked afterwards: "We lost a match and that is not to our satisfaction but it is not a drama.
"We are second. Everyone knows that this is 'the group' and that there are others that are jokes. Now we have two home matches and there are six points that are well within reach and could be enough get through to the second round."