Polymeric solid-solid phase change materials (S-SPCMs) are functional materials with phase transition-heat storing/releasing ability. With this respect, a series of polyethylene glycol (PEG) grafted styrenic copolymer were produced as novel S-SPCMs. PEGs with three different molecular weights were used for synthesis of isocyanate-terminated polymers (ITPs). To achieve cross-linking S-SPCMs, the ITPs were grafted with styrene-co-ally alcohol) (PSAA) at three different PSAA:PEG mole ratios. The produced polymers were characterized using Fourier transform infrared (FT-IR), proton nuclear magnetic resonance (H-1 NMR), and X-ray diffraction (XRD) technique. The crystalline-amorphous phase transitions of the polymers were examined using polarized optical microscopy (POM). The FT-IR, NMR, and XRD results confirmed the expected chemical structures and crystallization performances of the polymers. Thermal energy storage (TES) properties of the S-SPCMs were determined by differential scanning calorimetry (DSC). The DSC results revealed that the polymers with grafting ratio of PSAA:PEG(1:1) had phase transition enthalpies between about 74 and 142 J/g and phase transition temperatures between about 26 degrees C and 57 degrees C. Thermogravimetric analysis (TGA) measurements demonstrated that the S-SPCMs were resistant to thermal decomposition until about 300 degrees C. Thermal conductivities of the produced S-SPCMs were measured in a range of about 0.18 to 0.19 W/mK. Furthermore, TES properties of the S-SPCMs were slightly changed as their chemical structures were remained after 5000 thermal cycles. By overall evaluation of the findings, it can be foreseen that particularly PSAA-g-PEG(1:1) polymers can be considered as promising S-SPCMs for some TES practices such as air conditioning of buildings, thermoregulation of food packages, automobile components, electronic devices, and solar photovoltaic panels.