She was also the second woman to hold the office of Síndic d'Aran after her predecessor, Maria Pilar Busquets.
[1] In 1991, Serrano was elected to the Conselh Generau d'Aran, the governing legislature of the Val d'Aran, as a candidate from the Aranese Democratic Union (UDA) and the larger Aranese–Convergence and Unione electoral alliance.
Her colleague, Maria Pilar Busquets of the Aranese Democratic Convergence (which was also a member of the coalition at the time), was elected the first Síndic d'Aran.
Amparo Serrano filed a motion of no confidence against Busquets with the support of her own Aranese Democratic Union (UDA) and the Unity of Aran (UA) parties, successfully ousting Busquets.
Serrano became Síndic d'Aran, serving from 12 July 1993 until 7 June 1995.