The new sodium bis(1-methyl-1H-imidazol-2-ylthio)acetate, Na[(S-tim) 2 CHCO 2 ], has been prepared in ethanol solution using 2-mercapto-1-methylimidazole, dibromoacetic acid and NaOH. New di- and tri-organotin(IV) derivatives have been synthesized from reaction between SnR n Cl 4−n (R=Ph, Cy and n Bu, n=2–3) acceptors and Na[(S-tim) 2 CHCO 2 ]. Complexes of the type {[κ 1 O-(S-tim) 2 CHCO 2 ]SnR 3 } and related decarboxylated species {[κ 2 N,N-(S-tim) 2 CH 2 ]SnR 2 Cl 2 } have been obtained and characterized by elemental analyses, FT-IR, ESIMS and multinuclear ( 1 H, 13 C and 119 Sn) NMR spectral data. The adduct {κ 1 O-[(S-tim) 2 CHCO 2 ]Sn(H 2 O)(C 4 H 9 ) 3 } was characterized by single crystal X-ray studies. The dichloromethane reaction solution of {κ 1 O-[(S-tim) 2 CHCO 2 ]Sn(C 6 H 5 ) 3 } was re-crystallized and the decarboxylated species {[(S-tim) 2 CH 2 ]SnCl(H 2 O)(C 6 H 5 ) 3 } was obtained as a crystalline solid and characterized by X-ray crystallography.