A novel polymeric ionic liquid hybrid(PILH) film-modified electrode,in which the electrode surface is coated with a hydrophobic hybrid material composed of an ionene polymer with quaternary ammonium sites in its polymeric backbone and ionic liquids(Scheme 1),was fabricated by electropolymerization of N,N-dimethylaniline1 in a hydrophobic ionic liquid,which is able to be applied for electrogeneration of superoxide anion via one-electron reduction of O2 in aqueous media(Scheme 2).