Sergio has been playing guitar professionally since the age of 13. In 1993, He formed the band "Wando" with his siblings Rocío and Fernando Vallín. "Wando" won first place in the contest "Valores Juveniles Bacardí" in the group category with "Puedo gritarlo frente a ti". During a Luis Miguel concert, Sergio met guitarist Kiko Cibrián, to whom he gave a copy of his guitar demo. The demo passed from person to person until it reached Fher Olvera, Maná vocalist, who was looking for a guitarist. Pher was greatly impressed with Vallín's style, and asked him to audition. He was then chosen after trying out more than eighty guitarists and since 1994 has been an integral part of the band. Maná recorded Cuando los ángeles lloran in 1995, the first studio album with Sergio as lead guitar. Vallín has recorded four other studio albums Sueños Líquidos (1997), Revolución de Amor (2002), Drama Y Luz (2011), and Cama Incendiada (2015) as well as the Maná MTV Unplugged (1999).

Sergio's importance to the group has grown through the four albums. He debuted as a composer in Sueños Líquidos, with the flamenco influenced song "Ámame hasta que muera". He debuted as a singer in Revolución de Amor with the theme "¿Por qué te vas?" dedicated to his parents. In this album he also composed "No voy a ser tu esclavo" and collaborated again with Santana in the guitar solo of "Justicia Tierra y Libertad". In "Amar es Combatir" he wrote three songs: the cumbia "Somos Mar y Arena", "Relax", and "Bendita tu Luz". Sergio, who is considered one of the best Latin guitarists, is an admirer of flamenco musicians Paco de Lucía and Tomatito. He has worked as the producer of new artists like Chío and Serralde, and is currently working on the project "Escuela de Música México Contemporáneo".

Maná is an incredibly decorated band, having earned four Grammys, eight Latin Grammys, five MTV Video Music Awards, six Premios Juventud, 19 Billboard Latin Music Awards and 15 Premios Lo Nuestro awards. The band formed in 1986 and released its first album, Falta Amor, in 1990. In 1992, the group released ¿Dónde Jugarán Los Niños?, which sold more than 10 million copies worldwide (over 700,000 copies in the US alone) becoming the best-selling Spanish-language rock album of all time.

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