Jorge Jesus's side played out a goalless draw with Dynamo Kiev on the opening day, whereas Barca succumbed to a 3-0 defeat to Bayern Munich.
Match preview
In a game where no fewer than 20 shots were fired - 12 of which came from Benfica's attacking contingent - neither the Portuguese side nor Dynamo Kiev could break down the other's defence during a goalless stalemate on matchday one.
Jesus's men had to do it the hard way to book their spot in the group stages after a one-year absence - overcoming Spartak Moscow and PSV in the qualifying rounds - but they have not let their domestic fortunes take a hit as their perfect start to the league season continued at the weekend.
Summer signing Roman Yaremchuk bagged a brace before Joao Mario added gloss to the scoreline in a 3-1 success over Vitoria Guimaraes on Saturday - their seventh win from as many games in the 2021-22 Primeira Liga - and they have chalked up at least two goals in every game that they have scored in this term.
However, the two games in which they have failed to score this season have been their last two Champions League battles - both of which came away from home, though - and the Portuguese giants welcome Barcelona to a ground where they have won five out of five this term.
Jesus's men have also come up trumps in five of their last six Champions League games at the Estadio da Luz including qualifiers, and given Barcelona's wholly underwhelming start to the campaign, one would not put it past the hosts to keep that stellar run going.
With the pressure on his shoulders growing heavier by the week, under-fire Catalan coach Ronald Koeman saw his side blown away by Bayern on the opening matchday in the Champions League, as the Camp Nou crowd witnessed their side lose 3-0 to the German giants.
Thomas Muller broke the deadlock in the opening 45 minutes before Robert Lewandowski's second-half brace killed any hopes of a Blaugrana comeback, but the Catalan club at least head into Wednesday's game on the back of a morale-boosting league win.
Still unbeaten in the 2021-22 La Liga season, a youthful Barcelona side - one bedevilled by injuries, illnesses and suspensions - saw off Levante 3-0 on Sunday, as Memphis Depay and Luuk de Jong struck before Ansu Fati marked his comeback game with a goal 10 minutes after being introduced.
Barca ended a three-game winless run in all competitions with Sunday's triumph, but doubts persist over the long-term future of Koeman in the hotseat, in spite of reports claiming that the club cannot afford to sack the Dutchman at present.
Barca travel to the Estadio da Luz unbeaten in their last eight Champions League away games, though, and they have kept clean sheets in each of their last four meetings with Benfica, the most recent of which ended 0-0 at Camp Nou in the 2012-13 group stage.
Benfica Champions League form:
Benfica form (all competitions):
Barcelona Champions League form:
Barcelona form (all competitions):
Team News
Benfica defender Lucas Verissimo is back from a European ban this week and should displace fellow Brazilian Morato in the hosts' defence alongside Nicolas Otamendi and Jan Vertonghen.
Adel Taarabt is available for Champions League fixtures amid a lengthy domestic suspension, while Yaremchuk is under no pressure for a start up top as Haris Seferovic is expected to remain out until after the international break.
Pizzi and Everton are pushing for recalls to the wide areas, but the duo will have a hard time displacing Rafa Silva and Darwin Nunez for the visit of the Catalans.
Barcelona continue to cope without long-term injury victims Sergio Aguero, Ousmane Dembele and Martin Braithwaite, while Jordi Alba is also likely to miss out after coming off against Bayern, but Ansu Fati made his long-awaited comeback against Levante.
Alejandro Balde (back) and Sergi Roberto (gastrointestinal) are also uncertain, but recent reports have claimed that Pedri may be fit enough to return from a thigh problem in time for Wednesday.
Frenkie de Jong returns from a domestic ban and will displace Gavi or Nico Gonzalez in the visitors' midfield, while Sergino Dest will continue at left-back if Alba and Balde are both ruled out.
Benfica possible starting lineup:
Vlachodimos; Verissimo, Otamendi, Vertonghen; Pizzi, Weigl, Mario, Grimaldo; Silva, Yaremchuk, Nunez
Barcelona possible starting lineup:
Ter Stegen; Mingueza, Pique, Araujo, Dest; De Jong, Busquets, Pedri; Coutinho, De Jong, Depay
We say: Benfica 1-1 Barcelona
Despite claiming a vital three points at the weekend, Barcelona are far from full-strength and are not without their morale problems either, making this a more enticing affair than it would initially seem on paper.
One can only imagine what failure to win would do for Koeman's future in the hotseat, but an in-form Benfica will sense an opportunity at the fortress that is the Estadio da Luz and are more than capable of claiming a hard-earned point from this clash.