Gerard Pique and Cesc Fabregas were also among the Barcelona stars on show as the hosts recorded a 4-1 victory at the Olympic Stadium
Alba, Marc Bartra, Gerard Pique, Sergio Busquets and Cesc Fabregas all started at the Olympic Stadium in Barcelona, while Martin Montoya, Cristian Tello and Sergi Roberto were involved from the bench.
Bojan Krkic, on loan from Barca to Ajax, was amongst the goalscorers along with Osasuna striker Oriol Riera. Espanyol star Sergio Garcia was the star man after netting a double.
Alba said: “Playing with Catalonia was a very special night. We are happy with the win – congratulations to the team.”
Victor Valdes, Carles Puyol and Xavi are also regular participants for Catalonia but missed the game through injury.
The win meant former Barcelona midfielder Gerard tasted victory in his first game as coach after taking over from Johan Cruyff in 2013.
The region, who also play some matches at Camp Nou, do not have full independence from Spain so are not recognised by Uefa or Fifa, meaning they cannot currently play in official international competitions.
They do, however, regularly play friendly matches and La Liga’s winter break provides a rare opportunity to schedule fixtures in a packed club and international calendar.
Catalonia have also faced nations such as Argentina, Brazil, Nigeria and Colombia in recent years.
Despite tough opposition, they have now won four of their last six games and have only lost once in 11 matches since 2005.
Bartra added: "It was a great game and good to win with the Catalan national team. It is always a pleasure to take part.”
Sergi Roberto was also enthused by the victory over the African side and suggested a Catalonia side could perform impressively if they were awarded full international status.
He said: "Catalonia could compete at the highest level - you could see it in this game and Valdes, Xavi or Puyol were not even there!
“It was a good win and it is always special to play these games. Congratulations also to Oriol Rosell on making his debut.”