 Pye-Smith was the theological tutor at the Dissenting academy known as Homerton College near Hackney, London for forty-five years between 1805 and 1850.His pupils included Robert Halley, future Principal of New College, London; Samuel Dyer, the missionary; and William Johnson Fox of the South Place Chapel, later the South Place Ethical Society.Pye-Smith was minister of the Old Gravel Pit Chapel in Chatham Place, Hackney for nearly as long, from 1811–50.