The near‐band emission mechanism of GaP crystals with very low concentration of nonstoichiometric deep levels has been studied at high temperatures from 77 K to room temperature. Free‐exciton recombination with emission and absorption of momentum conserving phonons at the site of shallow impurities are first found in the 77‐K photoluminescence spectra, which has not been observed in the low‐temperature luminescence. Also, excitons bound to ionized shallow acceptors Zn are identified. The free‐exciton recombination increases as the temperature increases and becomes the dominant emission mechanism at room temperature, with no observable effects of nonradiative centers.