RB Leipzig were left rooted at the bottom of Group A after going down 5-0 against RB Leipzig at the Jan Breydel Stadium in Brugge.
Both teams have no chance of progressing to the last 16, as a double each from Christopher Nkunku and Emil Forsberg with Andre Silva getting the other finish helped the visitors to victory.
Liverpool made it five wins from five matches in Group B through a calm 2-0 victory over Portuguese giants FC Porto, who have their knockout hopes hanging by a threat.
The Reds entered halftime on level terms, but pegged the visitors back following the second half through Thiago Alcantara and then a late finish from Mohamed Salah.
Seven-time Champions League winners AC Milan got their first win on their return back to the tournament following a 1-0 victory over Atletico Madrid.
As the other contest in Group B and with Liverpool having won the group already, Junior Messias's late winner aided the Rossoneri to the win and in contention for second spot.
A ten-man Borussia Dortmund missed out on the knockout stages following a 3-1 loss against Sporting Clube, who advanced from Group C on the back of this victory.
The Black and Yellow must know settle for third spot, as a brace from Pedro Goncalves and a single finish from Pedro Porro helped the Portuguese outfit to victory.
Dortmund did pull a goal back in the closing minutes through Donyell Malen before they had Emre Can dismissed to end the match with ten players.
Real Madrid progressed to the knockout stages from Group D following a dominant 3-0 victory over the tournament debutants Sheriff Tiraspol.
Madrid also avenged the earlier loss suffered against the Moldovans at the Bernabeu and will be joined in the knockouts from Group D by Inter Milan following their win against Shakhtar Donetsk.
First half goals from David Alaba and then a belter from Toni Kroos aided Los Blancos, as Karim Benzema put the icing on the cake after the interval.
