In their first game following last season's promotion from the second tier, Espanyol earned a commendable point in a 0-0 draw away at Osasuna, while their visitors were held to a goalless draw at home to Granada.
Following their relegation from the top flight in the 2019-20 season, Espanyol had a strong campaign in the second tier last year, never dropping out of the top four.
Heading into the final stretch of the season, Vicente Moreno's side held third spot, but a run of eight victories from their last 13 games saw them rise to the summit of the division, eventually being promoted as champions.
As a result, they now head straight back into La Liga with the aim of avoiding the drop, and they started with a tough test away against Osasuna.
Moreno's men battled commendably, and came away with a point following a goalless draw, but the schedule does not get any easier as they take on the Europa League champions in their second La Liga outing.
Under Unai Emery, Villarreal had a fairly positive campaign last season, despite a slightly underwhelming seventh-placed finish in the Spanish top flight.
The Yellow Submarine progressed through the Europa League group stage with ease, only dropping two points, and cruised through the round of 16 with a 4-0 aggregate win over Dynamo Kiev.
Emery's side then knocked out Dinamo Zagreb before scraping past his former club Arsenal to get to the final, with a 2-1 home win and a resilient away performance to grind out a goalless draw.
Every outfield player for both sides converted their penalties, and Villarreal stopper Geronimo Rulli found the net before David de Gea missed his spot kick to hand the trophy to Villarreal, seeing Emery collect his fourth Europa League title.
While they narrowly lost to Champions League winners Chelsea after a penalty shootout in the European Super Cup, Villarreal headed into the new league season with confidence, but they may have felt slightly disappointed to be held to a goalless draw at home to Granada.
The Yellow Submarine had plenty of chances to net the winner but were unable to break the deadlock, and they will now look to put their first league win of the campaign on the board in their aim to improve on last season's seventh-placed finish while also pushing for another impressive continental campaign.
Espanyol come in with a clean bill of health, as Vicente Moreno should have a full squad to choose from.
Landry Dimata and Miguelon have both come through knocks and are available for Saturday's game, while the only question is over Manu Morlanes, who recently joined on loan from Villarreal and could be under an agreement to not make his debut against his parent club.
Raul de Tomas will lead the line hoping to open his account for the season after helping them to promotion with 23 league goals last campaign.
Villarreal come into the game without crucial midfielder Dani Parejo and winger Samu Chukwueze, while Pau Torres is likely to continue his rest after only recently concluding last campaign that included the Olympic Games.
Defender Juan Foyth was sent off for two yellow cards in the league opener against Granada, but one of those has since been rescinded, so he is available for Saturday's clash.
Winger Arnaut Danjuma is set to arrive from Bournemouth imminently, but is unlikely to be ready for this game.
Geronimo Rulli, who was primarily chosen in cup games last season, was surprisingly picked over Sergio Asenjo in the league opener, and Emery could be set to deploy Rulli as his first-choice stopper going forward.
Espanyol possible starting lineup:
Diego Lopez; V Gomez, Cabrera, S Gomez, Pedrosa; Darder, David Lopez; Embarba, Dimata, Puado; De Tomas
Villarreal possible starting lineup:
Rulli; Foyth, Mandi, Albiol, Pedraza; Pino, Trigueros, Capoue, A Moreno; Dia, G Moreno
We say: Espanyol 0-2 Villarreal
Espanyol started with a commendable result last week, but Saturday presents a much tougher test, and we see them falling short.
Despite failing to find the net last time out, Villarreal looked sharp going forward and remain strong at the back, and they should have enough to put their first win on the board against the newly-promoted side.