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Since the creation of the first solid-state laser, the search and investigation of single-crystal matrices appropriate for doping with rare-earth metals has not stopped. Reducing the overall dimensions of laser systems requires an increase in the concentration of activators in the matrix. Today, the most widely used in high-power solid-state lasers are materials based on sapphire doped with Er, Yb, Cr, Nd. However, with an increase in the activator concentrations causes a concentration quenching of the luminescence, which increases the generation threshold and reduces the lasing. Computer modeling of the structures of BPO4 doped with Ce, Tb, Yb has been carried out. BPO4 bulk crystals doped with Ce, Tb, Yb were obtained by the modified TSSG technique [1]. The analysis of the chemical composition of crystals was carried out by ICP-MS technique. The optical absorption of the samples was measured by the PCI method. The degree of crystal structure perfection was assessed by the method of scanning sectional topography and high-temperature X-ray diffraction technique. The luminescence properties of the polycrystalline samples as well as single crystal samples of BPO4:RE (RE= Ce, Tb, Yb) were investigated. [1] Guogang Xu, Jing Lib, Shujuan Han, Yongjie Guo, and Jiyang Wang Crystal Research and Technology, 2010, vol.4, pp. 1242–1244.