A series of polystyrene graft palmitic acid (PA) copolymers as novel polymeric solid-solid phase change materials (PCMs) were synthesized. In solid-solid PCMs, polystyrene is the skeleton and PA is a functional side chain that stores and releases heat during its phase transition process. The heat storage of copolymers is due to phase transition between crystalline and amorphous states of the soft segment PA in copolymer and the hard segment polystyrene restricted the free movement of molecular chains of the soft segments even above the phase transition temperature. The copolymers always remain in the solid state during the phase transition processing and therefore they are described as form-stable PCM. Fourier transform infrared spectroscopy (FT-IR) and polarization optical microscopy (POM) analyses were performed to investigate the chemical structures and crystalline morphology. Thermal energy storage properties, thermal reliability and thermal stability of the PCMs were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) methods. Thermal conductivities of the PCMs were also measured using thermal property analyzer. The analysis results indicated that the PA chains were successfully grafted onto the polystyrene backbone and the copolymers showed typical solid-solid phase transition properties. Moreover, thermal cycling test showed that the copolymers have good thermal reliability and chemical stability although they were subjected to 5000 heating/cooling cycling. The synthesized polystyrene-graft-PA copolymers as novel solid-solid PCMs have considerable potential for such as underfloor heating, thermo-regulated fibers and heating and cooling of agricultural greenhouses. Especially, the polystyrene-graft-PA copolymer including 75% PA is the most attractive PCM due to its highest latent heat storage capacity in the synthesized copolymer PCMs. (C) 2011 Elsevier B.V. All rights reserved.