The present study is focused on the effect of the TTABr/MX/H2O-nanoparticles on the rate of piperidinolysis of ionized phenyl salicylate where TTABr represents tetradecyltrimethylammonium bromide and MX = NaCl, NaBr and CnH2n+1CO2Na with n = 4, 5, 6 and 7. Pseudo-first-order rate constant for the piperidinolysis of ionized phenyl salicylate at 35°C and constant concentration [PSa(-)]T = 0.2 mM, [Pip]T = 0.1 M, [NaOH] = 30 mM, [TTABr]T and different [MX] follow an empirical relationship which gives two empirical constant, (X)kcat and K(X/S). The value of relative counterion (X) binding constant, RX(Br) were calculated from the relationship; RX(Br) = (X)kcat/(Br)kcat. The values of RX(Br) for X = C4H9CO2(-), C5H11CO2(-), C6H13CO2(-), and C7H15CO2(-) are increasing with increase in the number of alkyl chain of counterion X.