pH-sensitive viscoelastic fluids were obtained through the formation of wormlike micelles and hydrogels. These assemblies result from the 1:1 stoichiometric complex formation of acylglutamic acid (CnGlu) with tertiary alkylamine. The pH-sensitive nature reflects a change in the charge density around the CnGlu headgroups, controlling the curvature of the molecular assemblies. The longer chain CnGlu analogues yield the hydrogel in a narrow pH region. This study proposes a unique way to obtain stimulus-responsive viscoelastic fluids by means of gemini-like amphiphiles.