The mechanism of saponification Of structurally related and industrially important mono- and diesters in protic and aprotic solvent systems have been investigated. Time ratio method and Swain's standard data for series first order reactions have been utilized for the evaluation of rate data and thermodynamic parameters viz. DeltaE(not equal), -DeltaH(not equal), DeltaG(not equal), DeltaS(not equal) and logA for the steps which involve the competitive and consecutive saponification reactions. Further, the enthalpy-entropy correlations are used to establish the plausible mechanism of saponification process for the esters. Comparative study of the slopes of linear plots (DeltaH(not equal) vs. DeltaS(not equal)) reveal that dilaurates undergo faster saponification process than distearates and oleostearates irrespective of any solvent sytems. The experimental plots (DeltaH(not equal) vs. DeltaS(not equal)) support a faster saponification process of mono esters than diesters in all the protic and aprotic solvent systems studied.