PSG had won the French first division in each of the previous four seasons, but were stopped in their tracks by an impressive, young Monaco side this time around.
The Frenchman will serve a three-match ban, starting with the Wembley showpiece match against Chelsea on Saturday, following his dismissal for a reckless foul on Enner Valencia at the Emirates.
Doumoulin, the overall leader at the start of the stage, surrendered crucial time to his opponents after stopping for a comfort break with just 32km remaining in the 222km stage.
Marcelino said he would try to restore Valencia's standing in Spanish football as he was presented as the club's new coach on Tuesday, the latest in a succession of appointments.