Xavi's side, who have already won the title, suffered a 2-1 loss to Real Sociedad on Saturday evening, while Real Valladolid lost 2-0 at fellow strugglers Cadiz on Friday, and they now sit 18th in the table with three games left.
Match preview
Real Valladolid dropped into the relegation zone on Saturday when Getafe picked up a point against Elche, with Paulo Pezzolano's side currently 18th in the table, level on points (35) and games (35) with 17th-placed Getafe.
The White and Violets are struggling for points at the worst possible stage of the season, losing each of their last five games in Spain's top flight, including a 2-0 reverse at Cadiz on Friday night.
Real Valladolid picked up seven points from their three matches against Mallorca, Villarreal and Girona between April 9 and April 22, but they have lost every game since then, and it is set to be a fascinating end to the season for the club considering that their last two games are against Almeria and Getafe.
Pucela, who finished second in the Segunda Division last season to earn promotion, have the fourth-worst home record in La Liga this season, only picking up 24 points from their 17 games.
Real Valladolid have also lost each of their last six La Liga matches against Barcelona, including a 4-0 defeat in the reverse match at Camp Nou earlier this season.
Barcelona lifted the La Liga title on Saturday evening after securing the championship on May 14, but it was not quite the celebrations that the club had in mind, as they suffered a 2-1 defeat to Real Sociedad at Camp Nou.
Mikel Merino and Alexander Sorloth were on the scoresheet for Imanol Alguacil's side, and Robert Lewandowski's late goal only proved to be a consolation, as Barcelona lost for the fourth time in the league this season.
The Catalan outfit will take on Mallorca (H) and Celta Vigo (A) in their final two league games of the campaign, and they will want to end a hugely successful domestic season on a positive note.
Xavi's side have the best away record in Spain's top flight this season, picking up 40 points from their 17 matches on their travels, and they were 3-0 winners over Real Valladolid when they last visited the strugglers in the league in December 2020.
Barcelona's plans for the summer transfer window are well underway, with Lionel Messi their top target, and it will be fascinating to see whether the club can secure a return for the Argentine.
Xavi will also be determined to oversee an improvement in Europe next term, as the La Liga champions once again failed to make it through the group stage of the Champions League.
Real Valladolid La Liga form:
W
L
L
L
L
L
Barcelona La Liga form:
W
L
W
W
W
L
Team News
Real Valladolid will again be missing Luis Perez, Selim Amallah and Anuar Tuhami for Tuesday's contest through injury, while Martin Hongla is suspended following his red card against Cadiz.
Head coach Pezzolano is expected to resist the temptation to make wholesale changes to the side that started against Cadiz, but Alvaro Aguado and Lucas Olaza are likely to come into the XI.
There could also be a spot in the final third of the field for Gonzalo Plata, which could lead to a change of formation, with Pezzolano potentially being in an extra forward.
Barcelona, meanwhile, have Gavi available again after the midfielder missed out against Real Sociedad through suspension.
Pedri and Ronald Araujo were also both absent on Saturday due to minor muscular problems, and the pair will again miss out here, while Jules Kounde is also out due to a muscular issue of his own.
Ousmane Dembele is set to make a second successive start, having fully recovered from a hamstring problem which kept him out for an extended period, while Raphinha should also feature in the final third of the field despite pressure from Ferran Torres and Ansu Fati.
Real Valladolid possible starting lineup:
Masip; Fernandez, Sanchez, El Yamiq; Rosa, Monchu, Aguado, Olaza; Plata, Marin, Leon
Barcelona possible starting lineup:
Ter Stegen; Roberto, Alonso, Christensen, Balde; Gavi, Busquets, F de Jong; Dembele, Lewandowski, Raphinha
We say: Real Valladolid 1-2 Barcelona
This is a much bigger match for Real Valladolid than it is for Barcelona, as the home side are battling for their lives towards the bottom of the division. Xavi's side will be determined to bounce back from their loss to Real Sociedad, though, and we can see a narrow away success in this game.