Arriving in Aguascalientes, he had his first contact with music when he became part of a local student musical arrangement. At the age of ten he began to feel attracted to bands like The Beatles, The Rolling Stones, and The Doors. At thirteen, he received his first salary as a musician, when he began to give private guitar lessons to other young kids in his same age group. He formed the band "Wando" with his siblings Rocío and Fernando Vallín, and Emilio. "Wando" won first place in the contest "Valores Juveniles Bacardí" in 1993 in the group category with "Puedo gritarlo frente a ti". (Ana Bárbara won first prize in the singles category in the same contest).
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 for the band after the departure of Ulises Calleros and César "Vampiro" López. Olvera was greatly impressed with Vallín's style, and asked him to audition. Fher was very pleased with Sergio's audition, telling Sergio: "eres un bombon asesino", meaning "he's really good". Vallín was chosen after trying out more than eighty guitarists and since 1994 has formed part of Maná.
After a few collaborations with the band, doing covers of "Celoso" from Los Panchos and "Fool in the rain" from Led Zeppelin, 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).

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