After losing their opening two games of the season, including a 3-0 defeat to the Portuguese outfit in the reverse, the Catalans recovered to claim all six points against Dynamo Kiev.
The side now sits in second place, two clear of the Eagles, who were beaten 9-2 on aggregate by leaders Bayern Munich on matchday three and four.
The game also marks the first in Europe for new manager Xavi, who took over from Ronald Koeman after the Dutchman was given the boot last month.
His tenure began with a slender 1-0 victory over derby rivals Espanyol in La Liga on Saturday.
Barcelona vs Benfica Head-To-Head
Barcelona have beaten Benfica twice in their previous five games, although the Portuguese side secured a thumping 3-0 victory at home when the sides clashed in September.
Barcelona Form Guide (all competitions): L-D-W-D-W
Benfica Form Guide (all competitions): D-D-L-W-W
Barcelona vs Benfica Team News
The Catalans are going through an injury crisis right now.
Martin Braithwaite, Pedri, Ousmane Dembele and Ansu Fati are all out, while Sergio Aguero is recovering from a heart problem. There were even reports earlier this week that he might have to retire, although Xavi was quick to dismiss all such claims.
As if that wasn't enough, the side were dealt a triple injury scare at the weekend with Nico Gonzalez, Oscar Mingueza and Sergio Busquets all picking up knocks in the derby game against Espanyol.
However, none of them appeared serious and they might still feature on Tuesday.
Injured: Martin Braithwaite, Pedri, Ousmane Dembele, Ansu Fati
Unavailable: Sergio Aguero
Lucas Verissimo remains sidelined with a knee problem but Valentino Lazaro and Andre Almeida have recovered from their injuries in a selection boost for head coach Jorge Jesus.
Joao Mario has returned to training after struggling with a back injury but may not be risked, while Nemanja Radonjic is also set to miss out.
Injured: Lucas Verissimo, Nemanja Radonjic
Barcelona vs Benfica Predicted XI
Barcelona (4-3-3): Marc-Andre ter Stegen; Oscar Mingueza, Gerard Pique, Ronald Araujo, Jordi Alba; Gavi, Sergio Busquets, Frenkie de Jong; Sergino Dest, Memphis Depay, Philippe Coutinho.
Benfica (3-4-3): Odysseas Vlachodimos; Nicolas Otamendi, Morato, Jan Vertonghen; Gilberto, Pizzi, Julian Weigl, Alex Grimaldo; Rafa Silva, Roman Yaremchuk, Darwin Nunez.
Barcelona vs Benfica Prediction
Barcelona cannot afford to drop more points in the Champions League, especially considering their last fixture is away to Bayern Munich.
But with Koeman gone and a sense of renewed vigor pervading the Barcelona camp, you'd expect them to do much better than losing 3-0.
It will be tough, but the home side should narrowly seal all three points.
Prediction: Barcelona 2-1 Benfica