The influence of sodium impurity on photoluminescence (PL) spectra of ZnSe crystals doped during the growth process from Se melt has been investigated. PL spectra were measured in 430¸800 nm wavelength range, and 10¸100 K temperature range. The deconvolution of spectra was realized by Alentsev’ method. The radiation of exciton-impurity complexes (EIC) bounded to zinc vacancies native defects (I1 Vzn) (fig. (1)) is registered at 10 K in the near band edge PL spectrum of moderately doped ZnSe crystals. At the longer wavelengths, a broad band localized at 2.698 eV with phonon replicas is observed. This band includes three components: R, Q and P, which are absent in spectra of undoped crystals. The increase of the doping level leads to occurrence of the radiation band of EIC bounded to both donors, having the activation energy of 35±5 meV (I2 Na), and hydrogen-like acceptors, with activation energy of 110±10 meV (I1 Na) (fig. (2)). The increase of impurity concentration leads also to the increase of the relative intensity of R and P bands, to occurrence of FA band, and to disappearance of Q band. In hightemperature (100 K) PL spectra excited by pulse laser radiation, the band localized at 2.662 eV (O band) is observed also. The analysis of excitation power density influence on considered spectra allows one to attribute R, Q and P bands to donor-acceptor pairs (DAP) radiations. Annealing of the doped crystals leads to the decrease of impurity PL bands intensity due to the Na extraction from crystals. It is established, that similar extraction increases with the increase of the Zn vapors density in annealing medium. This observation allows one to conclude, that the sodium impurity in the ZnSe lattice is able to form both substitutional NaZn acceptor defects and interstitial Nai donor defects. The reduction of VZn density by annealing in medium with high density of Zn vapors, promotes the increase of quickly diffusing Nai centers against of NaZn defects. Data allowing one to conclude that Na impurity forms in the ZnSe lattice simple hydrogen-like acceptors of NaZn, having the activation energy of 105±3 meV, are discussed. These acceptors are responsible for radiative annihilation of EIC bounded to shallow acceptors (I1 Na), for electronic transitions from conductivity band to considered acceptors (FA), and also for DAP radiation bands (R, Q, P and O), which include centers of Nai (with the activation energy of 18±3 meV) as donor, uncontrollable donors (26±3 meV), NaZnVSe centers (35±3 meV) and NaiNaZn (52±9 meV), accordingly. Associative NaZnVSe donors are responsible also for the radiation of donor EIC (I2 Na).figuraFig. Near band edge PL spectra of ZnSe crystals grown at 920°С from melt of Se + х mol % Na. x = 0.1 (1), 3 (2). Т = 10 K. Excitation density is 10 mW/mm2 by He-Cd laser.