A novel solid–solid phase-change energy storage material was synthesized by the aqueous phase precipitation polymerization. The amphiphilic polyethylene glycol-maleic acid monoester macromonomer (MAPEG) with a double bond and a terminal carboxyl was the side chain and the polyacrylonitrile (PAN) was a skeleton. The chemical structure and thermal properties of the graft copolymer were investigated. The results indicated that the MAPEG chains were successfully grafted onto the PAN backbone. The graft copolymer possess good thermal reliability and the phase-transition temperature is in the temperature range of human comfort, meanwhile, the melting enthalpy could reach 74.16 J/g and the crystallization enthalpy could reach 65.40 J/g, accounting for theoretical enthalpy value of 89 and 93%, respectively. Besides, optimum conditions of synthesizing the graft copolymer were determined by orthogonal experiment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40152.