The novel polycrystalline phosphors BaBi_2-xEu_xB₂O₇ (x ​= ​0, 0.05, 0.10, 0.15, 0.20, 0.30, 0.40) were obtained by crystallization from glass-ceramics. Single-crystal X-ray diffraction experiments were provided for the x ​= ​0.10, 0.20 and 0.40 samples in order to investigate a distribution of the Eu³⁺ ions over cation sites. It is shown that the Eu³⁺ ions substitute the Bi³⁺ ones in the M1 and M2 sites. Luminescent properties of the BaBi_2-xEu_xB₂O₇ phosphors were investigated for the first time. The optimal concentration of the Eu³⁺ ions was revealed for the sample with x ​= ​0.40, after that an immiscibility of the BaBi_2-xEu_xB₂O₇ solid solutions occurs, which is of a structure-dependent nature. Increase of the Eu³⁺ content leads to a gradual change of chromaticity from light red to orange-red/red. It is expected that the BaBi₂B₂O₇:Eu³⁺ phosphors can be used as red-emitting ones under LED excitation.