And the Catalan team likely needs to beat group champions Bayern because Benfica, who are two points behind them in third place, are a big candidate in their last match at home against bottom club Dynamo Kiev.
But Bayern beat Barcelona 3-0 at the Nou Camp last September, beating them 8-2 on their way to the 2020 title, German news agency DPA reported.
Barcelona and Benfica are vying for one of the five spots remaining in the last 16 matches of the elite event in the final round on Tuesday and Wednesday.
The biggest excitement is in Group G, where the four teams have a chance when leaders Lille go to bottom of the table Wolfsburg and second-placed Salzburg face Sevilla, and Lille and Salzburg advance if they avoid defeat.
There is also plenty to play in Group B as Liverpool won all five matches, but former winners Porto, Milan and former runners-up Atletico Madrid are separated by one point.
Milan host Liverpool and will advance with a victory – after losing their first three games of the season – provided that Porto and Atletico draw.
Xavi Hernandez was a 20-year-old Barcelona player when he last failed to get past the group stage in 2000-01, with Bayern finishing fourth out of five titles that season.
Xavi is now Barcelona coach and faces a huge task in Munich against the Bundesliga champions who have not lost a point yet, such as Liverpool and Ajax.
Indebted Barcelona are far from their glory days and a 1-0 home defeat against Real Betis leaves them seventh in La Liga, 16 points off the lead.
It was Xavi’s first defeat at the helm, and he then admitted that “we have to compete like animals” in Munich for a chance to advance.
Barcelona at least won’t face a hostile crowd as the game is played behind closed doors due to the tighter coronavirus regulations in Bavaria.
But Bayern will want to show their dominance again a few days after winning the German Bundesliga title 3-2 at Borussia Dortmund which according to midfielder Leon Goretzka “was about bragging rights in Germany, and of course you want to get them”.
Bayern has similar ambitions in Europe and has already been confirmed as the group winner alongside Ajax, Liverpool, Manchester City and Manchester City.
Paris Saint-Germain and Sporting secured second place, while Chelsea, Inter Milan, Juventus and record champions Real Madrid reached the last 16 but places in their groups have yet to be decided.