Agnew was born in Glasgow in 1964. He attended Magdalen College at Oxford University as a choral scholar, performing in the school's famous chapel choir in addition to his academic studies. When he graduated, London's early music scene was burgeoning, and there were plenty of opportunities for a young singer. He performed in the Consort of Musicke and also sang at various times with the Sixteen, the Gothic Voices, and the Tallis Scholars choirs. Launching a career as a soloist in the early 1990s, Agnew attracted Christie's attention and was offered the chance to move to France to perform with Les Arts Florissants. He was soon the group's lead vocal soloist, performing lead roles in such operas as Rameau's Hippolyte et Aricie, in a production that traveled around France and as far as New York. Agnew was a tenor, but he also sang in a high register in a voice known in French as the haute-contre. He has sometimes been described as a countertenor as well as a tenor, but the haute-contre, of which Agnew was one of the few exponents when he began taking such roles in the 1990s, has a different vocal quality that involves less falsetto than a true countertenor voice. Although Agnew has devoted much of his career to Les Arts Florissants, he has also sung in English and has recorded a wide variety of material, including songs of Ivor Gurney and, in 2001, Beethoven's settings of English-language folk songs. He has also performed in large choral works by Bach and others, and recorded English voice and lute music with lutenist Christopher Wilson.
In 2007, Agnew began leading Les Arts Florissants as associate conductor; he began to conduct the group more and more often, and later he was named joint music director. In 2018, conducting Les Arts Florissants, he released an album devoted to little-known French Baroque motet composers Sébastien de Brossard and Pierre Bouteiller. ~ James Manheim, Rovi