The hosts were beaten 3-1 by their arch rivals at the Santiago Bernabeu on Sunday, while the visitors secured a much-needed 2-0 win over Osasuna.
Match preview
Prior to Sunday's defeat, Barcelona had been virtually unstoppable in LaLiga, winning seven consecutive games by an aggregate score of 20-1, since an opening-day stalemate with Rayo Vallecano.
Such imperious domestic form helped to set up a grandstand Clasico, with Xavi's men sitting at the top of the table, level on points with their formidable rivals going into the 250th edition of the historic fixture.
The opening goal at the Santiago Bernabeu on Sunday, from Ballon d'Or winner Karim Benzema, was the first that the Catalan side had conceded in 624 LaLiga minutes, but it only took Los Blancos another 23 to add a second, in a first-half display that swept the game out of reach.
While Ferran Torres was able to pull one back in the second half, an unusually blunt attacking performance from Robert Lewandowski saw the Blaugrana side struggle, and ultimately fail, to salvage a point, as Rodrygo Goes rounded off the win with an injury-time penalty.
Following a frustrating 3-3 draw with Inter Milan in the Champions League, it is now essential that the hosts do not let their confidence slip, with a selection of potential banana-skin league games falling either side of an all-or-nothing showdown with Bayern Munich.
Not only staring down the barrel of an early European exit, any lapse of concentration in LaLiga could see a ruthless Real Madrid pull away for good.
The visitors, on the other hand, will be hoping to build on an encouraging 2-0 win over Osasuna on Monday night, as Arnaut Danjuma scored his first league goals of the season with a well-taken brace.
Unai Emery's men were experiencing a slight dip in form following a strong start to the season, with uninspiring defeats to top four-chasing rivals Real Betis and Real Sociedad, alongside drab draws with Cadiz and Getafe, seeing the Yellow Submarine fall out of the European spots.
Nonetheless, having secured their passage through to the UEFA Conference League knockout stages, the club from Castellon looked back to their assured selves during their weekend win, with Alex Baena continuing to impress in the absence of talisman Gerard Moreno.
Villarreal actually recorded their first win over Barcelona in 27 attempts last season, with a 2-0 victory over Xavi's side at Camp Nou. The hosts have plenty more to play for this time around, though, and should present a much sterner test.
Barcelona La Liga form:
W
W
W
W
W
L
Barcelona form (all competitions):
W
W
L
W
D
L
Villarreal La Liga form:
W
L
D
D
L
W
Villarreal form (all competitions):
D
D
W
L
W
W
Team News
Barcelona will continue without long-term absentees Ronald Araujo, Memphis Depay and Andreas Christensen, as Xavi faces a few selection headaches after their Clasico display.
Ousmane Dembele and Eric Garcia would seem to be those most in danger of losing their starting positions, with Ansu Fati and Gerard Pique waiting in the wings.
For the visitors, Alberto Moreno made an emotional return to action on Monday after seven months out, and will provide an option from the bench once again at Camp Nou. Gerard Moreno, Francis Coquelin and Juan Foyth, on the other hand, all remain sidelined.
Unai Emery has so far been reluctant to utilise Jose Luis Morales in the league, despite grabbing six goals and three assists in European competition. Another lively performance off the bench against Osasuna, however, could see El Comandante included here.
Barcelona possible starting lineup:
Ter Stegen; Balde, Pique, Kounde, Roberto; Pedri, Busquets, Gavi; Fati, Lewandowski, Torres
Villarreal possible starting lineup:
Rulli; Pedraza, Torres, Albiol, Femenia; Parejo, Capoue, Lo Celso; Morales, Danjuma, Baena
We say: Barcelona 2-1 Villarreal
Desperate to keep up with Real Madrid, dropped points are simply not an option for Barcelona in the weeks following their Clasico defeat.
Villarreal will make it very awkward for the home side, but their superior firepower should see them through to a narrow win.