His tutors included Gérard Souzay, Carlos Chausson, Dalton Baldwin, Paul Schilhawsky, Gerd Türk, Ulrich Eisenlohr and Wolfram Rieger.

He studied choral and orchestral conducting under Pierre Cao, Eric Ericson, Klaus Arp and Luis Gorelick.

He has performed in Madrid, Barcelona, Israel, Budapest, Karlsruhe, Oviedo's Opera (Spain), Villamarta, Córdoba (Argentina), Malaga, Galicia (Spain), and at the International Festivals of Perelada and Granada, under conductors including George Pehlivanian, Alberto Zedda, Sebastian Weigle, Josep Pons, Josep R. Encinar and Álvaro Albiach.

On the concert arena he sings Bach's St Matthew Passion, St John Passion and Christmas Oratorio, Brahms' German Requiem, Mozart's Requiem, Haydn's Nelson Mass, Schubert's Die schöne Müllerin and Winterreise, and Schumann's Schwanengesang and Dichterliebe.

Martínez-Castignani was nominated for a Grammy Award for the first recording of Xavier Montsalvatge’s El Gato con Botas.