A series of poly(styrene-co-p-stearoyl styrene) copolymers as novel polymeric solidsolid phase-change materials (SSPCMs) were synthesized by the modification of polystyrene with stearoyl chloride. The chemical structure and crystalline morphology of the synthesized copolymers were determined with Fourier transform infrared spectroscopy and polarized optical microscopy, respectively. The thermal energy storage properties and thermal stability of the SSPCMs were investigated with differential scanning calorimetry and thermogravimetric analysis, respectively. In addition, the thermal conductivity of the SSPCMs was measured with a thermal property analyzer. Moreover, thermal cycling tests showed that the copolymers had good thermal reliability and chemical stability after being subjected to 5000 heating/cooling cycles. The synthesized poly(styrene-co-stearoyl styrene) copolymers as novel SSPCMs have considerable potential for thermal energy storage and temperature-control applications. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012