Desio's spell in Galicia outlasted that of Aimar, but in December 1996 he moved to second-tier UD Salamanca where he played only until the end of that season; the team finished as runners-up and were promoted, but Desio would remain at the same level, joining Deportivo Alavés. Earning respect for his combative approach and ball-winning abilities, he immediately helped the Basque club achieve their own promotion as winners of the 1997–98 Segunda División, and alongside a new arrival with a similar style, compatriot Martín Astudillo, played regularly as the side coached by Mané narrowly maintained their status in the top division, qualified for the UEFA Cup and then reached the final of the European competition in successive years – Desio made 12 appearances in the continental run, which included the elimination of Inter Milan, and played the entirety of the 2001 UEFA Cup Final which Alavés lost 5–4 to Liverpool.