Abstract The complexes Ph 3Bi(MeOx)X (MeOx = 2-methyl-8-quinolinolato; X = Cl, Br), PhBi(MeOx) 2 and PhBiOx 2 (Ox = 8-quinolinolato) have been prepared and characterized by electronic, IR and 1H NMR spectra. The crystal structure of Ph 3Bi(MeOx)Cl was determined by single-crystal X-ray diffraction from diffractometer data. Crystal data: C 28H 23NOClBi, monoclinic, space group P2 1/ n, a 17.05(1), b 13.89(1), c 10.51(1) Å, β 97.30(3)°, V 2468 Å 3, Z = 4, D calcd 1.70 g cm −3; R = 0.078, 3048 observed reflections. The complex is monomeric, and the molecules are well separated, with the metal atom in a distorted octahedral coordination environment. The metal atom makes with the bidentate ligand a BiO bond of 2.19(2) Å and a relatively weak BiN bond of 2.71(2) Å.