The Liga champions, who are chasing their sixth Champions League title, will be eager to make an impact in the 2018-19 edition after being knocked out at the quarter-final stage last season.
PSV, meanwhile, have returned to UEFA's premier club competition after failing to qualify last term.
|Game||Barcelona vs PSV|
|Date||Tuesday, September 18|
|Time||5:55pm BST / 12:55pm ET|
TV Channel, Live Stream & How To Watch
In the United States (US) the game will be available to watch live on television via TNT USA or Univision and it can be streamed live online using Watch TNT, B/R Live or Univision NOW.
|US TV channel||Online stream|
|TNT USA / Univision||Watch TNT / B/R Live / Univision NOW|
The game can be watched live on television in the United Kingdom (UK) via BT Sport 1 and it can be streamed live online using the BT Sport app.
|UK TV channel||Online stream|
|BT Sport 1||BT Sport app|
Squads & Team News
|Goalkeepers||Ter Stegen, Cillessen, Pena, Ezkieta|
|Defenders||Semedo, Pique, Lenglet, Rafinha, Alba, Umtiti, Vermaelen, Miranda, Cuenca|
|Midfielders||Rakitic, S. Busquets, D. Suarez, Arthur, Samper, Roberto, Vidal, Alena, Puig, Monchu, Collado, O. Busquets|
|Forwards||Coutinho, L. Suarez, Messi, Dembele, Malcom, Munir, Ruiz|
Valverde will have a near-full panel to choose from, with Denis Suarez likely to be fit enough to take a place in the squad, but Sergi Samper is injured.
Nelson Semedo began the weekend's game against Real Sociedad at right-back but was taken off at half-time and Sergi Roberto, who has played there this season, has been preferred.
Philippe Coutinho, who came on at the beginning of the second half in that contest, will earn the start, his first for Barcelona in the Champions League after he was unable to feature for them last year.
Barcelona XI: Ter Stegen; Alba, Pique, Umtiti, Roberto; S. Busquets, Rakitic, Coutinho; Dembele, Messi, L. Suarez.
|Goalkeepers||Zoet, Room, Van Osch|
|Defenders||Isimat-Mirin, Behich, Viergever, Schwaab, Angelino, Obispo, Sainsbury, Dumfries, Teze, Soulas|
|Midfielders||Pereiro, Hendrix, Rigo, Rosario, Ramselaar, Lundqvist, Gutierrez, Thomas, Sadilek, Mauro Junior, Frey|
|Forwards||De Jong, Romero, Lozano, Malen, Bergwijn, Gakpo, Aboukhlal|
The likes of Ramon-Pascal Lundqvist, Ryan Thomas, Dante Rigo and Maximiliano Romero are injury concerns and unlikely to play. Van Bommel will be relying on stars such as Hirving Lozano, Luuk de Jong and Steven Bergwijn for goals.
PSV XI: Zoet; Dumfries, Schwaab, Viergever, Tasende; Hendrix, Pereiro, Rosario; Bergwijn, Lozano, De Jong.
Betting & Match Odds
Barcelona are serious favourites to win at 1/9 according to bet365 . PSV's chances of victory are rated at 25/1 and a draw is deemed more likely at 11/1.
Despite steering Barcelona to Liga glory in impressive fashion, Valverde could not crack the Champions League as his side crashed out against Roma in the last eight, despite taking what appeared to be an unassailable 4-1 lead in the first leg.
As he looks to build on the foundations laid in his first full season at the helm of the Catalan club, continental success will surely be high on the agenda.
The former Real Betis boss has added greater depth to his squad, recruiting players such as Arthur, Clement Lenglet, Malcom and Arturo Vidal, which should go some way towards helping the team manage what can often become a gruelling schedule, particularly heading into the latter stages of the competition.
"We prioritise everything, we will always fight for the Champions League," Valverde told reporters back in August when asked about where his focus lay.
"Barca will always be like that, we are very excited but the way to win the Champions League is to win the league. You focus on being better for a year, and if so, you are closer to winning the Champions League."
They get things started with a home match against a youthful PSV team, which is managed by former Barca midfielder Mark van Bommel and contains the talented Hirving Lozano, who has previously been linked with a move to Catalunya .
Sterner tasks are sure to come with Tottenham and Inter also competing in Group B, but they cannot afford to take the Eredivisie champions for granted.