Mestre spent his entire professional career from 1956 to 1969 with Valencia, making 323 La Liga appearances, a club record surpassed by Ricardo Arias 20 years later.

Mestalla, before having his first-team call-up on 15 January 1956 for a 4–2 home win over UD Las Palmas in La Liga, under manager Carlos Iturraspe.

[3] The third round against another Scottish club, Dunfermline Athletic, went to a play-off after a 6–6 aggregate draw, and Mestre scored the only goal of the decider at the Estádio do Restelo in Lisbon.

[10] At the end of the 1975–76 La Liga season the club hired Paraguayan Heriberto Herrera, who left in February 1977 and succeeded by Mestre for the remainder of the campaign.

[11] Mestre's third spell in charge began in January 1982 after the resignation of Pasieguito;[12] he received the job permanently in July after negotiations for César Luis Menotti, the 1978 FIFA World Cup-winning Argentina manager, broke down.