The effect of dielectric constant of medium on protonation equilibria has been studied by determining protonation constants of ethylenediamine pH metrically in various concentrations (0 -60%vyv) of acetonitrile -and ethylene glycol -water mixtures, at an ionic strength of 0.16 mol L À 1 and at 303.0 K. MINIQUAD75 computer program has been used for the calculation of protonation constants. Linear and non-linear variations of step-wise protonation constants with reciprocal of dielectric constant of the solvent mixtures have been attributed to the dominance of the electrostatic and non-electrostatic forces, respectively. The trend is explained on the basis of solute -solute and solute -solvent interactions, solvation, proton transfer processes and dielectric constants of the media.