Toluene-3,4-dithiolate complexes, [CH 3 C 6 H 3 S 2 As{S 2 P(OR) 2 }] and [CH 3 C 6 H 3 S 2 AsS 2 POGO] (R = o-, m-, p-C 6 H 4 Me; G = -CH 2 C(CH 3 ) 2 CH 2 -, -CHCH 3 CH 2 (CH 3 ) 2 C-), have been synthesized by reaction of toluene-3,4-dithiolatoarsenic(III) chloride [C 6 H 3 (CH 3 )S 2 AsCl] with ammonium salts of the corresponding O,O'-ditolyl/alkylene dithiophosphate by refluxing in benzene followed by stirring. These complexes have been characterized by elemental analysis and IR, 1 H, and 31 P NMR spectroscopy. Single-crystal X-ray diffraction analysis of [CH 3 C 6 H 3 S 2 As{S 2 P(OC 6 H 4 Me-m) 2 }] revealed distorted trigonal-bipyramidal geometry with an anisobidentate chelating mode of the ditolyl moiety in these complexes.