Results of electrical, optical, electron spin resonance and optically detected magnetic resonance studies of thermal neutron irradiated and annealed at 800 °C n-type GaP are presented. Evidence is found to support the view that the main dopant introduced via transmutation of GaP, germanium, occupies cation sites and forms neutral donors. This confirms the possibility of neutron transmutation doping of GaP. Simultaneously, it is shown that germanium is absent at cation sites. Presence of other forms of Ge-related defects is deduced from luminescence and absorption data. Some of them are tentatively identified as VGa-GeGa acceptors leading to the self-compensation process. This observation means that the neutron transmutation as a doping method in application to GaP is not as efficient as for Si.