The two sides will meet in the last eight of this year's competition, with the first leg set to take place at Old Trafford tomorrow.
It is the first time the European heavyweights have crossed paths since the 2011 final, which saw Barca lift the trophy after a 3-1 win at Wembley.
Pogba is expected to start the match, despite suffering an alarming drop in form over the last month, with no goals in his last seven appearances.
The Frenchman initially enjoyed a resurgence when Solskjaer took the reins at the Theatre of Dreams in December, but his recent issues have coincided with a poor run of results for the Red Devils.
United have lost three of their last four matches across all competitions and are now in real danger of missing out on a place in the Premier League's top four.
However, Solskjaer expects Pogba to rediscover his match-winning touch against Barca, as he told a press conference on Tuesday: "It is not about one player.
"Every player has to perform at the top level. At his best Paul can run a game like this.
"Paul’s job is to be the creator, to drive forward. Of course, I expect him to perform tomorrow."
The Red Devils dispatched Paris Saint Germain in the previous round of the Champions League after a stunning comeback in France.
Similar heroics could be required against the Spanish champions over the next fortnight, who are currently chasing a treble after all but sewing up the Liga title with a 2-0 win over Atletico Madrid on Saturday.
One major distraction for a number of United players, however, could be ongoing contract talks, with the likes of David de Gea, Juan Mata and Ander Herrera all approaching the final months of their current deals.
Summer exits have been touted, but Solskjaer is adamant that issues behind the scenes will not affect his squad heading into the clash with Barca.
The United boss responded when asked if negotiations could affect the players: "Not at all, we are all focused on this game.
"Talks will just go on, everyone is focused on the game tomorrow knowing we can create a special atmosphere.
"We will need the crowd in a game like this. Hopefully, a bit of rain will make for a special evening."