Carlos Soler opened the scoring in Valencia's 2-1 win with Phil Jones' calamitous second-half own goal proving too much for Mourinho's side.
Juan Mata had United's first effort of the game 26 minutes in and was unlucky not to win a penalty, with Mouctar Diakhaby clearly blocking the goal-bound shot with his arm, before Paul Pogba somehow prodded wide with the goal at his mercy following a corner. Valencia, who were already assured of third place and qualification for the knockout stages of the Europa League, finished with eight while Young Boys earned four.
Porto would probably be the favoured pick but, on this evidence, they might feel the same about United.
Soler spoke of his annoyance that United secured their last-16 spot with a controversial Marouane Fellaini victor against Young Boys, and he played here like a man determined to show his team deserved to go through.
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"I think that to qualify in this group is a success", Mourinho said.
The Red Devils came into the game knowing a victory would see them finish top of the group above Juventus, thus avoiding a tricky last 16 clash with one of the competition's group winners. He was so risky in the first half that Marcos Rojo was hauled off at half-time.
United's task in turning the game around became significantly harder thanks to a clumsy moment from Jones, who failed to communicate properly with team mate Sergio Romero and slid the ball into his own net.
"It's job done in a hard group", Mourinho told BT Sport.
The Belgian forward was referring to the many times Jones has been caught on camera displaying rather unique facial expressions.
Substitute Marcus Rashford pulled a goal back three minutes from time but it was not enough to take advantage of Juventus' slip up.