Reaction of triphenylbismuth with 4-nitrophenylacetic and 2-nitrobenzoic acids provided phenylbismuth bis(4-nitrophenyl)acetate and diphenylbismuth 2-nitrobenzoate. According to the XRD data, bismuth atoms have distorted octahedral and trigonal-bipyramid coordinations. Tridentate carboxylate ligands play role of chelates.Keywords: phenylbismuth bis(4-nitrophenyl)acetate, diphenylbismuth 2-nitrobenzoate, X-ray analysis An interest to investigation of the synthetic approaches to bismuth carboxylates is explained by their use as precursors to finely crystalline bismuth oxide, heterometallic bismuth-contained oxides for segnetoelectric materials and catalysts [1,2], and as biologically active compounds [3][4][5][6].