The visitors will enter the contest off the back of a 2-2 draw with Genoa in Serie A, while Braga suffered a 3-1 defeat to Farense in the Primeira Liga last time out.
Match preview
Braga finished third in the Primeira Liga last season, which saw them secure a position in the third qualifying round for the 2023-24 Champions League.
Os Arcebispos, in their first Champions League fixture since 2012, beat TSC 3-0 in the first leg of their third qualifying round contest, before running out 4-1 winners in the reverse match to secure a 7-1 success.
Braga then navigated their way past Panathinaikos in the playoff round, winning 2-1 in Portugal before recording a 1-0 victory in the reverse match in Greece, so their performances in this season's competition have been impressive.
Artur Jorge's side will also face Union Berlin and Real Madrid in Group C, and they will be determined to make the perfect start to their group-stage campaign on Wednesday, but the Portuguese outfit will enter the contest off the back of a disappointing result, having lost 3-1 to Farense in the league on Saturday.
Braga, who are eighth in their domestic division with seven points from five matches, last played in the group stage of the Champions League in 2010-11, finishing third to drop into the Europa League, and they actually made the final of that competition before losing to Porto.
Napoli, meanwhile, will enter the contest off the back of a 2-2 draw with Genoa in the league on Saturday, and a total of seven points from four matches has left them in fifth spot in the Serie A table.
The Blues won their third Serie A title last term and their first since 1990; the team are in the group stage of the Champions League for a second year in a row, progressing to the quarter-finals last season.
Napoli's last-eight spot in 2022-23 was the best that they have performed in the European Cup, and Rudi Garcia's side will be expecting to advance to at least the knockout round of this season's competition.
The Italian champions will host Real Madrid in their next game in the section ahead of a trip to Union Berlin, and it will be fascinating to see how Group C unfolds, as Real Madrid and Napoli are the favourites, but both Union Berlin and Braga are capable of causing a surprise.
Garcia's team, who have picked up just one point from their last two league games, will seemingly once again be looking to Victor Osimhen for goals this season, and the 24-year-old has already netted three times during a strong start to the campaign.
Braga Champions League form:
Braga form (all competitions):
Napoli form (all competitions):
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Team News
Braga will be without the services of Sikou Niakate through injury, but the home side are otherwise in excellent shape heading into their opening group-stage fixture.
Bruma and Alvaro Djalo have netted eight times between them in the early stages of the season, and the pair will once again feature in the starting side for the Portuguese outfit.
Simon Banza has two goals to his name, with the 27-year-old likely to be given the nod in the final third, while Ricardo Horta is also expected to be included in the starting side.
As for Napoli, Pierluigi Gollini is out with a hand injury, but the visitors are otherwise in strong shape, and there are not expected to be any real surprises in their XI for this match.
Osimhen will once again operate through the middle, with the talented Khvicha Kvaratskhelia playing off the left; Matteo Politano came off the bench to score against Genoa, meanwhile, and the 30-year-old could also be a part of the front three on Wednesday night.
A three-man midfield will include Piotr Zielinski and Stanislav Lobotka, while Juan Jesus is set to be joined in the middle of the defence by Leo Ostigard.
Braga possible starting lineup:
Matheus; Gomez, Oliveira, Fonte, Borja; Moutinho, Musrati; Horta, Djalo, Bruma; Banza
Napoli possible starting lineup:
Meret; Di Lorenzo, Jesus, Ostigard, Olivera; Zielinski, Lobotka, Anguissa; Politano, Osimhen, Kvartskhelia
We say: Braga 1-1 Napoli
Napoli will be the favourites on Wednesday night, but Braga are a very talented side, and this will not be a straightforward match for the Italians, who have dropped points in their last two league matches. It would not be a surprise to see an away win, but we are backing the points to be shared in this contest.