The interaction between imidazole (L1), 2-isopropylimidazole (L2), 2-amino-benzimidazole (L3) and 2-(2-pyridyl)benzimidazole (L4) (L in general), and dimethyltin chloride in water have been investigated at 25 degrees C and ionic strength of 0.1 M sodium nitrate using the potentiometric technique. The results showed the formation of 1:1 and 1:2 (organotin:ligand) complexes and the corresponding stability constants were determined. The effect of the pKa values of the respective ligands on the stability constants of its complex species was elucidated. The concentration distribution of the complexes in solution was evaluated. Also, their solid complexes of the general formula in diethylether-dichloromethane, give 1:2 (organotin:Ligand) [(L)2 (CH3)2 SnCl2.zH2O][L = L1, z = 0 and L = L2, z = 1] and 1:1 [L (CH3)2 SnCl2.zH2O][L = L3, z = 0 and L = L4, z = 2]. The separated solid products were characterized by elemental analyses (C, H, N, Cl), IR, mass spectra, thermogravimetric analysis (TGA) and magnetic susceptibility. The participation of the ligand functional groups in bonding to the organotin (IV) was discussed. Conductivity and 1H-NMR spectra were used to confirm the behaviour of these complexes in solution.