Photocapacitance spectra of the excitation probability of electrons (or holes) occupied in deep levels have been measured for S‐ and Te‐doped nitrogen‐free GaP light‐emitting diodes grown by temperature difference method of liquid phase epitaxy under various phosphorus pressures in the vicinity of the optimum pressure (Popt). A band at 2.00 eV observed for the diodes grown under phosphorus pressures higher thanPoptis attributed to interstitial phosphorus atoms. On the other hand, bands at 2.10 and 2.20 eV which were observed, respectively, in the spectra of S‐ and Te‐doped diodes grown under phosphorus pressure lower thanPoptare attributed to complex centers of phosphorus vacancies and donors.