The experienced defender was caught up in an ugly confrontation between players and fans prior to the continental encounter in Portugal.
During the warm-up, the Marseille squad approached the end of the stadium housing their away following.
With tempers boiling over, Evra launched a kick towards the head of one of those to have approached the playing field.
Evra was given a straight red for his involvement in the unsightly scuffle, immediately ruling him out of the contest and leaving him facing further punishment.
The 36-year-old had not been named in Marseille's starting XI but was due to take his place among the substitutes.
He must now wait and see what UEFA make of his actions as he awaits an inevitable sanction.
Evra is now the owner of an unwanted piece of history, having become the first player be sent off from a Europa League match before kick-off.
0 - Patrice Evra is the 1st player to receive a red card before the kick off of a game in the history of the EL (2009/10). Karateka. pic.twitter.com/9Ii92bLnU7— OptaJean (@OptaJean) November 2, 2017
Marseille had entered their meeting with Vitoria unbeaten in their last five games in all competitions.
Evra, meanwhile, has been restricted to just nine appearances this season.