Smith began his musical career as a chorister at Westminster Abbey, where he often appeared as a treble soloist; he performed with the group at the BBC Proms and other nationally prominent events. He went on to Bedford School, where he was a music scholar (performing at school events in return for reduced tuition), and then to a gap year singing with the Winchester Cathedral Choir, performing as a soloist with the Wayneflete Signers, and joining the staff of the Pilgrims' School. Smith earned a Specialist Early Music Performance degree at the Schola Cantorum Basiliensis, where he studied voice with countertenor Andreas Scholl and bass Ulrich Messthaler. He also sang in the Royal School of Church Music's Millennium Youth Choir. A stint in the Britten-Pears Young Artists Programme helped launch his varied career, conducting the Voces Cantabiles choir and making solo appearances in Handel's Messiah, HWV 56, Bach's St. John Passion, BWV 245, and a semi-staged production of Handel's dramatic oratorio Saul, HWV 53. Conducting Voces Cantabiles, Smith made his recording debut on the Naxos label in 2007 with an album of works by Robert Parsons.
In 2003, Smith and his brother Paul Smith founded VOCES8. The group took shape as friends from the Millennium Youth Choir continued to gather and sing after they aged out of the group; they traveled to Switzerland on a lark for a competition and ended up winning. VOCES8 is unusual in its composition, with six male singers, including two countertenors (Barnaby Smith being one) and two women. VOCES8 has performed around Britain, the U.S., and continental Europe. Smith continues to serve as artistic director. He maintains his solo career and has performed across Britain and in such prestigious international halls as the Muziekgebouw Amsterdam, the Elbphilharmonie Hamburg, and Mariinsky Theatre Concert Hall. He has led major orchestras as a conductor, including the Philharmonia Orchestra, the English Chamber Orchestra, and the London Philharmonic. Smith has conducted VOCES8 on some 15 recordings and has appeared as a conductor or countertenor on various other projects. He is also in demand as a choir trainer and educator, having been co-curator of the Master's program in singing at Cambridge University. In 2021, Smith led VOCES8 on the Naxos album Infinity. ~ James Manheim, Rovi