Time-resolved photoluminescence (TRPL) at T=4,2K, electron paramagnetic resonance (EPR) in the range of 4,2K–77K, and wavelength modulated transmittance (WMT) spectra for both undoped and annealed in Bi and Zn melts ZnSe single crystals have been investigated. It is found that the annealing in Bi melts leads to recovery of crystal structure. This supposition is based on the increase of fine and hype fine interaction of residual Mn2+, ions with the simultaneous decrease of the EPR signals line width and the decrease of the F-center line. Furthermore, the band with λmax=520 nm disappears, while exciton band I1 (λmax=445 nm) and edge band Q0 – DAP (λmax=460,2 nm), involving AlZn – LiZn, pairs, become more revealed. At the same time, band narrowing of the TRPL spectra was observed. The annealing in Zn melt causes the increase of the number of F-center. From WMT spectra the energy position of local centers and the dominant influence on impurities and defects of the crystal structure were investigated.