We report changes in the photoluminescence spectra associated with the diffusion of Cu in CdTe thin films used in CdTe/CdS solar cells. Films grown by vapor transport deposition and radio-frequency sputtering as well as single crystal CdTe were included in the study. The main effects of Cu diffusion appear to be the quenching of a donor-acceptor transition associated with Cd vacancies and the increase in intensity of a lower energy broad-band transition. The PL is subsequently used to explore the effects of electric fields on Cu diffusion. The role of Te as a diffusion barrier for Cu is investigated. ©1999 American Institute of Physics.