Copper ions form impurity defects in ZnSe crystals making series of associates with native crystal lattice defects [1]. At the same time, incorporated Yb ions concentrate in their neighbour uncontrolled background impurity in the ZnSe crystal lattice [2], which gives an “purifying” effect and can be observed, for example, in increasing of edge band intensity. In this case, it is interesting to investigate combined formation of impurity complexes by ytterbium and copper ions in the ZnSe crystals. The series of samples of the ZnSe crystals doped separate and mix with Yb and Cu ions were obtained. Yb ions were incorporated in the ZnSe crystal lattice during the growth process and Cu ions – by thermal diffusion from the layer which had been deposited on the crystals surface. Photoluminescence (PL) spectra were investigated in the 400-3000 nm spectral range and at 77 and 300K temperatures. The intensity of the edge band increases both at 77K (Fig.) and room temperature by adding Yb impurity in ZnSe and ZnSe:Cu crystals. This effect is known as “purifying” effect by Yb ions from background impurities [2]. The bands appear with maxima at 530, 980 and 1650 nm in the longwave of visible and IR spectral regions. The band at 530 nm is the most intense in the ZnSe:Cu crystals where the CuZn 2+ ion substitutes zinc and forms acceptor energy level. In visible PL spectra is observed another PL band with 640 nm peak, which associates with formation of donor-acceptor pair (DAP) and Cu2+ ions as acceptor (Fig. inset). PL bands do not change their position while the temperature is changing and it is characteristics of intracentered transitions (Fig.). Doping with Yb ions results in vanishing DAP-radiation, shifting 530 nm PL band and registration of 2 μm band in the favour of multiplied amplification of discussed (edge, 980 and 1650 nm) PL bands. Process of impurity associates formation by Yb and Cu ions in the ZnSe crystals are analized.