After an abysmal start to the campaign, previous Valencia head coach Carlos Corberan was relieved of his duties, with the 1-0 defeat to Sevilla at the weekend proving to be the final straw.
However, with a new era underway and plenty to prove, the visitors thought they had taken the lead shortly after the quarter-hour mark when Arnaut Danjuma’s first-time effort beat Antonio Sivera and sneaked inside the post, only for VAR to rule the goal out for offside.
This served as something of a wake-up call for the Babazorros, and they created a few efforts of their own in response, the best of which saw Pablo Maffeo’s volley from just outside the area gathered by Sivera.
Alaves had made their joint-best start to a top-flight campaign, having collected 10 points from their opening five matches, and their confidence was clear to see as they continued to grow into the first half.
They could have even found the opener shortly before half time when Angel Perez’s cross into the area was headed wide by Pablo Ibanez.
A relatively entertaining first half provided plenty of promise that something similar would follow after the break. Instead, though, both sides struggled to settle into any attacking rhythm.
All three of Alaves’ victories so far this season had come at home, but they were unable to rediscover the offensive flair they displayed in their most recent game in front of their own supporters, a 5-2 win over Osasuna.
Valencia, meanwhile, were hardly threatening themselves, but even a share of the spoils would have been a significant sign of progress after their recent troubles.
However, with just over 10 minutes remaining, the visitors found an unlikely winner to send their travelling support wild.
A precise through ball from Javi Guerra played in Luis Rioja, who broke into the area and lifted over Silvera to snatch the points for Valencia and help his team climb out of the relegation zone, for the time being at least.
While the result is a disappointing one for Alaves, especially as it means they miss out on the chance to record four successive home victories for the first time since 2001, they remain in fourth place thanks to their overall strong start.
Flashscore Man of the Match: Luis Rioja (Valencia)