Barcelona were incredibly dumped out of the competition by Roma in the quarter-finals last season, and will be desperate for more European glory having watched rivals Real Madrid's domination in recent years.
Spanish champions for a 25th time last season, Barcelona have started the 2018-19 campaign in fine form, overcoming Sevilla to win the Spanish Super Cup early last month, before making a perfect start to their La Liga title defence.
It appears that the Catalan giants will once again be the team to stop in Spain this term, but there is no question that the club will be desperate to lift the Champions League having watched bitter rivals Real claim the trophy in each of the last three campaigns.
Barcelona have not actually won the European Cup since 2015, and were incredibly eliminated by Roma in the quarter-finals last term. The club recorded a 4-1 victory in the first leg of their last-eight affair, but suffered a 3-0 loss in Italy to lose on away goals in spectacular fashion.
Barcelona will fancy their chances of getting off to a positive start considering that they have not lost at home in the Champions League for five years. What's more, the Spanish club have won their group in each of the last 11 seasons, and have been victorious in all of their home group games in the last five editions.
Group B is very interesting when considering that Inter Milan and Tottenham Hotspur are also in the section, and Barcelona will know that their two games against PSV will be vital when it comes to progression.
Not since September 2013 have Barcelona lost a Champions League match in front of their own supporters. The Spanish outfit have only beaten PSV at home on one occasion back in 1978, however, and will be wary of the threat that the Dutch champions could provide on Tuesday night.
Recent form: WDWWL
Recent form (all competitions): WWWWW
Dutch champions PSV will be aware of their underdog status entering Wednesday's clash with Barcelona, but there is no question that the Red and Whites will be confident of causing an upset due to their wonderful form this term.
PSV claimed their 24th Eredivisie title last season, and have made a blistering start to the 2018-19 campaign, winning their last seven matches in all competitions. As expected, they top the Dutch league at this stage, and have beaten Willem II 6-1 and thumped ADO Den Haag 7-0 in their last two matches.
Barcelona are one of a number of clubs believed to be closely monitoring the attacker Hirving Lozano, who impressed for Mexico at the 2018 World Cup. Lozano has already scored six times in all competitions this term, and will be looking to show his ability at Camp Nou this week.
This will be PSV's 16th season in the group stage of the Champions League, and they qualified having overcome BATE Borisov 6-2 on aggregate in the playoffs. They have only reached the knockout round of the competition on four occasions, however, the last of which came during the 2015-16 season.
PSV have also failed to win in their last eight Champions League group fixtures, and did not triumph in their last group-stage campaign, which came during the 2016-17 season. Their last away win in the competition was in November 2007, and their record in Spain is also very worrying ahead of this match.
Indeed, the Dutch outfit have lost nine of their 14 European fixtures away to La Liga opposition - failing to win in the process - and have not beaten Spanish opposition home or away since December 2003.
This match will also see a Barcelona return for Mark van Bommel, who replaced Phillip Cocu as PSV boss in June. The 41-year-old won the Champions League and La Liga title as a player during his only season (2005-06) at Camp Nou, and will be hoping to upset his former employers on Tuesday night.
Recent form: WWWWW
Recent form (all competitions): LLDWW
Barcelona boss Valverde left Sergio Busquets and Philippe Coutinho out of his starting XI for Saturday's La Liga clash with Real Sociedad, but the pair are expected to return to the XI for this match.
Dembele has now scored in each of his last three appearances for Barcelona as the Frenchman settles into life at Camp Nou, and will now looking to make an impact in the Champions League.
PSV, meanwhile, will enter the match off the back of a thumping 7-0 win over ADO Den Haag in the league at the weekend.
Barcelona possible starting lineup:
Ter Stegen; Roberto, Umtiti, Pique, Alba; Busquets, Coutinho, Rakitic; Dembele, Suarez, Messi
PSV possible starting lineup:
Zoet; Dumfries, Schwaab, Viergever, Angelino; Rosario, Pereiro, Hendrix; Lozano, L de Jong, Bergwijn
Head To Head
Tuesday will be the seventh meeting between Barcelona and PSV in European competition. Barcelona lead the head-to-head two wins to PSV's one, with three of their six matches ending in draws. The pair last locked horns in the group stage of the 1997-98 Champions League, and both matches finished level.
Barcelona and PSV have also previously met in both the semi-finals and quarter-finals of the UEFA Cup, with PSV progressing from their last-four match-up in 1978, and Barcelona from their 1996 quarter-final two-legged affair.
We say: Barcelona 3-1 PSV
PSV have started the 2018-19 campaign in fine form, but they have not come up against a team with Barcelona's quality, and the Dutch outfit could be in for a tough night at Camp Nou.
We fancy the visitors to get their name on the scoresheet due to their quality in the final third of the field, but expect Barcelona to open their group-stage campaign with a win.