The work is devoted to the synthesis and attestation of a number of substituted vanadates and chromates of bismuth. For bismuth vanadates of the BIMEVOX family, the homogeneity regions of the Bi4V2 – xCr x O11 ± d solid solutions have been refined, the features of the structure change of the compounds with increasing chromium content and changing temperature have been noted, and the powders and ceramics have been studied by electron microscopy. For the first time, as an impurity, an individually substituted bismuth chromate of the composition Substituted bismuth chromate of the Bi13Cr5 – yV y O34.5 – d (y = 0.95 ± 0.05) composition has been detected for the first time as an impurity and synthesized as an individual compound, which has been characterized by X-ray diffraction, electron microscopy, chemical analysis, and photoelectron spectroscopy data; its homogeneity range has been determined, and electroconductive characteristics have been studied.