A new type of ester-based cationic surfactant having a quinuclidinolium headgroup has been synthesized starting from linear fatty alcohols and has been characterized using spectroscopic techniques. The self-aggregation and thermodynamic properties of these surfactants have been investigated by pendant-drop surface tensiometry and conductivity measurements. The liquid crystalline behaviors of these surfactants were investigated by small-angle X-ray scattering (SAXS) technique. The quinuclidinolium headgroup demonstrated a unique ability to interlock among themselves thus affecting the physicochemical properties of surfactants in aqueous solution. The current research finding supports the new concept of headgroup interlocking which is supported by 1D and 2D NMR studies.