Due to the large direct bandgap energy (Eg = 2.82 eV at 4.2 K), zinc selenide is an attractive semiconductor material for development and fabrication of numerous devices such as light emitting diodes, X-ray scintillators and ultraviolet photodetectors [1]. Using different kinds of doping impurities in zinc selenide, it is possible to control the type of conductivity (n-type or p-type). The growth of p-type ZnSe crystals is a challenging issue. They may be obtained by using Sb impurity as a dopant. During the doping process, the Sb impurity fills the Se vacancies and forms the acceptor centers with activation energy varying from 70 to 600 meV. In this work, we report the results of low-temperature (10 K) luminescence of ZnSe(I) and ZnSe(I):0.1 at.% Sb crystals grown by chemical vapor transport method with iodine as a transport agent. A 325 nm Cd-He laser is used as an excitation source. The photoluminescence (PL) spectra of ZnSe(I) and ZnSe(I):Sb crystals recorded with a HORIBA 750M monochromator and shown in Fig. 1. The lines at 442.6 nm and 441.4 nm are dominant in the PL spectra of as-grown ZnSe(I) crystal and may be assigned to the donor-bound exciton and free exciton, respectively. Sb-doping of ZnSe(I) crystals lead to intensity decrease of a near-band-edge emission. The line at 443.5 nm is dominant in the PL spectra of these samples and may be attributed to Sb-based acceptor-bound exciton. The activation energy of Sb-based acceptor estimated from the PL spectra of ZnSe(I) and ZnSe(I):0.1 at.% Sb samples is equal to 114 meV. The mechanisms of radiative recombination and the nature of the centres responsible for the near-band-edge PL of the investigated undoped and Sb-doped ZnSe(I) crystals are discussed.