The company has this month installed a total of 700 A3 wall-mounted panels to 50 trains which link Edinburgh, Glasgow, Aberdeen and Inverness.
First ScotRail, which has not sold advertising space on its trains before, carries six million passengers a year between Glasgow and Edinburgh. The route is the busiest in Scotland and is used by a large number of ABC1 commuters.
Peter Williams, head of marketing at First ScotRail, said: "The average time spent by customers travelling on a train is 42 minutes, making the panels an ideal opportunity to expose brand advertising messages."
Viacom signed a contract with parent company First Group in 2004 and already operates advertising on station platforms.
The outdoor company announced this week that advertising revenues for its rail division grew by 72% year on year.