Protic ionic liquids (PILs) have been attracted growing attention due to their remarkable physicochemical characteristics. It is still imperative to improve the conductivity of PIL for actual applications. Herein, we have studied non-stoichiometric PILs based on 2-aminoethyl hydrogen sulphate triflate via dielectric relaxation spectroscopy, showing significantly enhanced conductivities, which are strongly coupled to the structural relaxation as manifested by VFT-behaviour.