Xavi's side finished their La Liga season on Sunday evening with a 2-0 home defeat to Villarreal and will now face A-League All Stars, who are back after an eight-year absence.
A-League All Stars faced Manchester United and Juventus in 2013 and 2014 respectively, and the team will now make it a historic treble by taking on Barcelona in Sydney on May 25.
A 30-man squad has been selected for the contest, with fans voting for the first 13 players, while coach Dwight Yorke and A-Leagues Commissioner Greg O'Rourke were also involved in naming the final squad.
Former Manchester United striker Yorke was confirmed as the A-League All Stars head coach last month, but there will be some key absentees for the hosts, as players that reached the A-League grand final, which will see Western United face Melbourne City, will not be involved.
The team lost 5-1 to Man United in their first ever fixture before suffering a 3-2 defeat to Juventus, and those involved in the post-season contest will be keen to show the strength of Australia's top flight.
It was a disappointing finish to a difficult season for the Catalan outfit, but they had managed to secure second spot win the La Liga table ahead of the contest, and Xavi has given the fans plenty of reasons to be positive about next season, as they attempt to finish at the summit once again.
Barcelona have confirmed friendlies against Inter Miami and New York Red Bulls for the end of July, and it remains to be seen whether Xavi selects a strong side for this contest.
A lack of European football in recent weeks means that the Catalan outfit have not had a crowded fixture list, though, and it could provide a final opportunity for some out-of-favour players to convince Xavi that they should be a part of the squad for the 2022-23 campaign.
Barcelona are said to be planning a busy summer transfer window despite their financial problems, with Bayern Munich's Robert Lewandowski still being strongly linked with a switch to Camp Nou, while a number of unwanted players will also be moving on in the coming months.
A 30-man A-League All Stars squad was confirmed on May 20, and every side in the A-League Men will have at least one player in the team.
Nestroy Irankunda, 16, and Garang Kuol, 17, will be hoping to be given opportunities to impress, but as mentioned, those involved in the A-League Men grand final will not feature, so the home side will be without some potentially key players for the contest.
Former Everton and Manchester City midfielder Jack Rodwell plays for Western Sydney Wanderers and could start against Barcelona, but Yorke will make full use of his squad over the contest.
As for Barcelona, Gerard Pique, Pedri, Sergio Roberto, Eric Garcia and Sergino Dest will all miss the contest through injury, while Riqui Puig and Oscar Mingueza are out, having been named in the Catalan national team squad to take on Jamaica.
Ferran Torres, Martin Braithwaite, Neto and Clement Lenglet will also not be making the trip, but the likes of Sergio Busquets, Pierre-Emerick Aubameyang, Jordi Alba, Dani Alves and Marc-Andre ter Stegen should all be involved in the post-season contest.
Adama Traore is also set to feature in what could be his final game for the club, with the Spaniard potentially returning to parent club Wolverhampton Wanderers this summer.
A-League All Stars possible starting lineup:
Kurto; Traore, Davidson, Grant, Miranda; Penha, Ninkovic, Rodwell, O'Shea; Goodwin, Cummings
Barcelona possible starting lineup:
Ter Stegen; Alves, Araujo, Umtiti, Balde; Gavi, Busquets, F de Jong; Traore, Memphis, Dembele
We say: A-League All Stars 1-3 Barcelona
A-League All Stars have a number of talented players and will be looking to showcase their abilities in the friendly contest, but Barcelona's superior quality should ultimately shine through to secure a relatively comfortable victory.
For data analysis of the most likely results, scorelines and more for this match please click here.