Zinc selenide scintillation crystals isoelectronically doped with aluminum and oxygen by introducing Al2O3 into the charge were grown, and their emission was studied under photo- and X-ray- excitation, and comparison of their emission properties to those of the conventional scintillator ZnSe(Te) was accomplished. It is demonstrated that this technique for oxygen introduction enables the formation of oxygen-related deep donor–acceptor pairs (DAPs) acting as radiative recombination centers in ZnSe(O,Al) up to the densities exceeding the density of the corresponding Te-related DAPs in ZnSe(Te) at the doping level of 1wt%. ZnSe(O,Al) exhibits a higher photoluminescence intensity than that in ZnSe(Te) because of more efficient light absorption, while the photoluminescence quantum yield and the emission intensity under X-ray excitation show an opposite trend.