In our recent reports, we have shown that when a poly(ethylene glycol) (PEG) chain is covalently linked to any ionic group, the resultant molecule behaves like an amphiphile. Depending upon the nature of ionic head groups, they self assemble to form micelles or vesicles, in which the PEG chain constitutes the micellar core or vesicle bilayer. In this study, we intend to examine what happens when both hydrocarbon (HC) and PEG chains are attached to a carboxylate head group. Therefore, we have synthesized two novel amphiphiles in which a PEG and a HC chain is covalently linked to L-cysteine. The surface activities and the solution behavior of the sodium salts of these amphiphiles were investigated at neutral pH. The amphiphiles self organize to form large unilamellar vesicles in dilute solutions, which transformed into small micelles at higher concentrations. The HC chains of the molecules have been shown to constitute the bilayer membrane of the vesicles and core of micelles. In acidic pH, the amphiphiles were found to form:large disklike Micelles. The thermodynamic parameters of self-assembly formation were also measured by isothermal titration calorimetry. The vesicle and micelle: formation was found to be spontaneous and thermodynamically favorable. The thermal stability of the micelles at neutral and acidic pH was studied. The addition of cholesterol was observed to increase the physical stability of vesicles.