The Schiff bases [H2SBSaD], [H2SBVD] and [H2SBND], derived by the condensation of S‐benzyldithiocarbazate and salicylaldehyde, 2‐hydroxy‐3‐methoxybenzaldehyde and 2‐hydroxy‐1‐naphthaldehyde respectively, react with diestertin dichlorides, R2SnCl2 [R=CH2CH2CO2CH3, CH2CH2CO2C2H5 or CH2CH2CO2C4H9] in 1:1 molar proportion to yield chlorine‐substituted complexes of the type R2Sn(Schiff base), the base being tridentate. The complexes are characterized on the basis of their elemental analyses, IR and 1H NMR spectral studies. The 13C and 119Sn NMR and the tin‐carbon coupling constant data reveal the structures of the complexes to be octahedral with trans ester grouping, and bidentate ester linkages. The pentacoordinated complex (CH3)2Sn(SBSaD) was prepared by the reaction of dimethyltin oxide with H2SBSaD in equimolar proportions.