Real Madrid had to come back from 2-0 down to grab a 2-2 draw at home to Club Brugge, while Shakhtar stunned Atalanta in stoppage time.
Dennis Bonaventure's double gave the visitors a shock 2-0 advantage at half time, and the Belgians missed a huge chance to kill it off at 3-0 in the early stages of the second.
Sergio Ramos dragged Real Madrid back into the contest ten minutes after the interval, before the crucial minute of action just six minutes from time saw Ruud Vormer sent off for Brugge and Casemiro head the hosts level from the resulting free kick.
The Belgian side held out for the final few minutes with ten men to claim a famous point and leave Real Madrid without a win in three straight Champions League home games.
While Real are currently sitting top of LaLiga, they are at the foot of their group, where PSG are top after making it two wins from two later in the evening by edging out Galatasaray 1-0.
Mauro Icardi bagged his first PSG goal since joining on loan from Inter Milan, with the Argentinian left with the simplest of tap-ins seven minutes after the resumption when he was teed up by Pablo Sarabia.
Goals from Gonzalo Higuain, Federico Bernardeschi and Cristiano Ronaldo helped Juventus beat Bayer Leverkusen 3-0, while Group D rivals Atletico Madrid defeated Lokomotiv Moscow 2-0 thanks to Joao Felix and Thomas Partey.
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