The effect of some added electrolytes, viz. NaCl, CaCl2 and AlCl3, on the critical micelle concentration (CMC),maximum surface excess concentration (Γmax) and minimum area per molecule (Amin) at air-liquid interface of a cationicsurfactant cetylpyridinium chloride (CPC) in aqueous solutions have been studied at 288.15, 293.15 and 298.15 K usingtensiometric method. The effect of an added electrolyte on decreasing CMC of CPC is found to be in the order (AlCl3) >(CaCl2) > (NaCl), which falls in the same order as of the moles chloride ions furnished by each mole of the addedelectrolyte. The Γmax decreases with increasing temperature and electrolyte concentration leading to an enhanced availablearea per molecule at the air-liquid interface. The process of micellization and adsorption of CPC at air-liquid interface areboth favoured by exothermic enthalpy change as well as entropy gain. The observed features such as lowering of CMC,higher thermodynamic micellar stability, more relaxed surfactant molecules at the interface, due to an added electrolyte,may be exploited for improving the efficiency of the surfactant as a detergent, solubilizing agent, froth floatation process forconcentrating ores, petroleum oil recovery and oil spill management.