AbstractA new amphiphilic quaternary random ionomer (PIDHES) was used to construct self‐assembly films. PIDHES was prepared by a selective ionization of quaternary random copolymer, poly(N,N‐domethyl amimethyl methartylate‐co‐2‐hydroxypropyl methacrylate‐co‐2‐ethylhexyl acrylate‐co‐styrene) precursor, which was synthesized by free radical copolymerization of commercial hydrophilic monomers N, N‐domethyl amimethyl methartylate and 2‐hydroxypropyl methacrylate and hydrophobic monomers 2‐ethylhexyl acrylate and styrene PIDHES could self‐assemble into polymer micelles in water, which underwent orientated deposition in the electric field and ultimately produced secondary assembly films. Scanning electron microscopy studies showed that the resultant PIDHES secondary assembly film was smooth and compact. Moreover, it was found that PIDHES micelles concentration and electric‐field‐induced time had a strong influence on the morphologies of the resultant secondary assembly film. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013