We have used deep level photoluminescence spectroscopy to investigate the surface electronic quality of molecular beam epitaxy (MBE) grown CdTe layers during ultrahigh vacuum cleaning. Spectra are highly sensitive to heat treatment, contamination, and electron beam exposure. The technique provides a guide to growth and cleaning of MBE films of optimal electronic quality, which exhibit intense near‐band‐edge and minimal deep level emission and which exceed substantially the electronic quality of bulk CdTe crystals.