Valencia's shock 2-1 win over Rangers at Ibrox in the Champions League Group F means the Spaniards go top and are guaranteed to progress to the second phase and leaves Rangers with a mammoth task if their are to make the second phase of the League.
Bayern Munich and Rangers play each other in Munich next Wednesday when Dick Advocaat's men must draw or win to progress.
In Eindhoven PSV, despite a disappointing European campaign, showed in the first half why they are top of the Dutch first division.
Ruud van Nistelrooy sidefooted the hosts ahead against Bayern into an open goal after a delightful Dutch move had sliced through the German defence.
But Paraguayan striker Roque Santa Cruz - the world's most expensive teenager - squared the match for the German champions six minutes after the interval.
Belgian international Luc Nilis struck the winner for PSV after 57 minutes.
Galatasaray's stunning 4-1 win away to Hertha Berlin, leaves Group H wide open.
Chelsea now top the group ahead of Hertha on goal difference with eight points.
Wins over Milan and Chelsea had possibly made Hertha overconfident and Galatasaray, 5-0 losers against Chelsea in Istanbul, made them pay.
The Germans made a solid start and went ahead on 35 minutes through a penalty from Norwegian Kjetil Rekdal but Hakan Sukur equalised three minutes after the break and suddenly the Germans lost their way catastrophically.
Thereafter it was all Galatasaray and Sukur, Kerimoglu Tugay and Buruk Okan completed a comprehensive victory. In Group E, though, it is all over bar the shouting. FC Porto and Real Madrid have qualified at the expense of Greece's Olympiakos and Norway's Molde.
Group G is also wrapped up. Sparta Prague's 0-0 draw at Bordeaux was enough to see the Czechs join the French champions, who had secured their place last week.
Spartak Moscow's 1-1 home draw with Willem II of Holland was not enough to see them keep the contest with Prague for the second place alive.