A new series of ester functionalized cationic gemini surfactants having different cationic headgroups (i.e. piperidinium, pyrrolidinium, morpholinium and quaternary ammonium) have been synthesized and characterized using NMR and Mass spectroscopy. These new gemini surfactants were investigated for their micellization and viscosity properties using surface tension, conductivity, fluorescence and rheology thechniques. The physicochemical properties of the aqueous surfactant system were influenced by polarity, size and the nature of cationic headgroups as the surface, thermodynamic and viscosity properties of these gemini surfactants were found to be dependent on the type of cationic headgroup. The current research finding establishes the structure-property relationship of the surfactant molecule specifically taking into account the dominant role displayed by the nature of the cationic headgroup.