The hosts finally scored their first goal, and remarkably, sealed their first win of the season before the international break, while the visitors were held to a 1-1 draw by Sevilla at their temporary home, the Ciutat de Valencia.
Match preview
Before kickoff in Valladolid two weeks ago, Sergio Gonzalez's Cadiz were the only side yet to score in Europe's top five leagues, with their goal difference of -14 amounting to the joint worst of all 98 sides, alongside Bochum.
Yet, as a scrappy game trudged into its 92nd minute, a misjudged punch from Real Valladolid keeper Sergio Asenjo presented veteran striker Alvaro Negredo with the simplest of finishes.
Their first shot on target in over three games, the visitors dramatically secured their first points of the season, with one of the final kicks of the game.
Nonetheless, the euphoria of that sensational smash-and-grab cannot completely mask what has been a dire start to the season for Los Piratas, with resounding 4-0 defeats to both Barcelona and Athletic Bilbao continuing a worrying trend of poor performances at home, with just three wins in their last 23 matches in front of their own fans.
One of those victories, however, did come against Villarreal, securing a 1-0 win over Saturday's opponents back in March, having held them to a dramatic 3-3 draw at the Estadio de la Ceramica earlier that campaign.
While Cadiz were not able to score at the start of this campaign, Villarreal were, at one point, the only side in Europe's top five leagues yet to concede. A 1-0 defeat to Real Betis three weeks ago saw that record collapse, however, along with their seven-game unbeaten run.
Unai Emery's men followed up their first LaLiga defeat since May with a 1-1 draw against Sevilla before the international break, as Alex Baena continued his magnificent goalscoring form to cancel out Oliver Torres's eighth-minute strike.
While the Yellow Submarine might have been disappointed not to take all three points against struggling opponents, the side cannot be too dissatisfied with their start to the season, with the breakout performances of the aforementioned Baena, alongside Nicolas Jackson, proving to be particularly pleasing for the Castellon club.
Following two consecutive seventh-place finishes, the goal for Villarreal is to maintain league consistency alongside European commitments.
With three defeats in six league games against last season's relegated sides, a trip to Cadiz represents exactly the kind of game that Emery's side needs to be winning on most occasions, in a very competitive race for the top four.
As a gruelling October schedule begins for Villarreal, a game without complications against relegation-threatened opponents would be very welcome indeed.
Cadiz La Liga form:
L
L
L
L
L
W
Villarreal La Liga form:
W
W
D
W
L
D
Villarreal form (all competitions):
D
W
W
L
W
D
Team News
The international break offered valuable recovery time for a host of key players for Cadiz, with the likes of Ruben Alcaraz and Alex Fernandez working hard to put persistent injuries behind them once and for all.
Striker Anthony Lozano sat out the late win at Real Valladolid, but could be in contention to return against Villarreal, against whom he scored a hat-trick last season.
For the visitors, star player Gerard Moreno remains a doubt with a hamstring injury, while Samuel Chukwueze, who missed Nigeria's game with Algeria, might be fit enough to make the bench after receiving a knock against Sevilla.
Club legend Manu Trigueros and important defender Juan Foyth are also both doubtful, while Alberto Moreno is still out with an anterior cruciate ligament tear suffered last season.
There could be a return for Arnaut Danjuma, though, after he made an encouraging 30-minute cameo before the international break.
Cadiz possible starting lineup:
Ledesma; Espino, Chust, Hernandez, Zaldua; San Emeterio, Alcaraz; Ocampo, Fernandez, Alejo; Lozano
Villarreal possible starting lineup:
Rulli; Pedraza, Torres, Albiol, Femenia; Lo Celso, Parejo, Capoue, Pino; Baena, Danjuma
We say: Cadiz 1-3 Villarreal
Villarreal are no strangers to dropping points in winnable games, having lost and drawn to Saturday's opponents last season.
Nonetheless, after the consistent start that Unai Emery's side have made, with the added incentive of getting back on track after recent dropped points, the visitors should be too strong.