Reactions of triorganotin chlorides with potassium salt of O-alkyl trithiophosphate [ROP(S)(SK)(2); R = Me, Pr-i, Ph] in 2:1 molar ratio in anhydrous benzene yield triorganotin O-alkyl trithiophosphate of the type ROP(S) [SSnR'(3)](2) R = Me, Pr-i ; Ph, R' = P(r)n, Bu-n, Ph] which are found to be monomeric in nature. These complexes are soluble in common organic solvents. Similar reactions of diorganotin chloride with dipotassium salt of S-alkyl trithiophosphate yield diorganotin-S-alkyl trithiophosphate of the type [(RS)P(O)S-2](2)SnR2; R = Me, Pr-i; R' = Me, Et, Ph, which also are found to be monomeric in nature and are soluble in common organic solvents. The newly synthesized derivatives have been characterized by physicochemical and spectroscopic techniques, IR, NMR H-1 (31)p, and Sn-119).