A new complex, {Bi(III)[S2CN(CH2C6H5)(2)](3)}(2)center dot 2CH(3)CN, was synthesized and characterized by elemental analysis, IR, TG, H-1 NMR and X-ray single-crystal diffraction. The complex crystallizes in the triclinic system, space group P (1) over bar, with a = 12.705(6), b = 13.430(6), c = 15.489(12) angstrom, alpha = 102.135(12), beta = 99.649(12), gamma = 111.521(9)degrees, Z = 1, V = 2315(2) angstrom(3), D-c = 1.531 g.cm(-3), F(000) = 1068, mu = 4.116 mm(-1), the final R = 0.0559, wR = 0.1069 and S = 1.056. The coordinated geometry of Bi(III) with six sulfur atoms from three ligands is a distorted pentagonal pyramidal configuration, and the structural system is formed by weak interactions of Bi center dot center dot center dot S between two molecules. The complex was valued for its antibacterial activity by agar-streak method. It was found that the complex is weakly active against three of the five tested bacterial organisms.