Ultraviolet photoemission spectroscopy is used to investigate the development of negative electron affinity at the surface of hydrogenated Zn-doped InP (100). Hydrogen injected into the material electronically passivates the local carrier concentration. Reverse-biased anneals of the InP under ultrahigh vacuum show a dramatic change in the work function of the material within a set annealing temperature range suggesting the establishment of negative electron affinity at the surface. The strength of the negative electron affinity is 1.08eV. This value is consistent with the deactivation energy of the H–Zn complex (1.14eV) determined previously. Spectral features are also shown to be sensitive to sample temperature. Hydrogen retrapping at the surface limits the effect and it is dependent on whether the surface is smooth or roughened. The electron affinity of the material is thus controlled with defect density and annealing temperature.