High-quality and large-size p-ZnSe single crystals doped with antimony (Sb) have been grown by a Bridgman method using a closed double crucible. Photoluminescence spectra at low temperatures indicate that Sb works as both a shallow acceptor and a deep complex donor. By studying the temperature and excitation intensity dependences of the free-to-acceptor and donor-acceptor pair emissions, we estimated that the ionization energy of Sb as a shallow acceptor in ZnSe is (112–114)meV above the valence band, and that of the deep complex donor related to Sb is 37 ±1meV below the conduction band.