The 33-year-old is likely to make his second debut for the club on Saturday in the Intertoto Cup final against Bulgarian outfit Cherno More.
"He will be on the bench and, although I will be putting the interests of the team first, I want to give him his debut," said Sampdoria coach Walter Mazzarri.
After an unsuccessful loan spell with Fulham last season, Montella will be hoping to rediscover his form at the Luigi Ferraris Stadium and he is fully aware of the significance of Saturday's game.
"The important thing is qualifying," said Montella.
"I still have a lot of football left in me - important games - but this game means a hell of a lot to Sampdoria."