The interaction of trimethyltin(IV) (TMT) with imino-bis(methylphosphonic acid) (IDP), abbreviated as H4L, was investigated at 25 °C and at ionic strength 0.1 mol⋅dm−3 (NaNO3) using a potentiometric technique. The formation constants of the complexes formed in solution were calculated using the nonlinear least-squares program MINIQUAD-75. The stoichiometry and stability constants are reported for the complexes formed. The results show the formation of 110, 111, 112 and 11-1 complexes for the TMT–IDP system. The concentration distribution of the various complex species was evaluated. The effect of dioxane as a solvent, on both the protonation constants and the formation constants of trimethyltin(IV) complexes with IDP, is discussed. The thermodynamic parameters ΔH∘ and ΔS∘ calculated from the temperature dependence of the equilibrium constants were evaluated. The effect of ionic strength on the protonation constants of IDP is also discussed.