Thermal degradation of polystyrene/ZnO (PS/ZnO) nanocomposites was investigated in this study. PS/ZnO polymer nanocomposites were prepared by using ZnO nanorods as nanofillers that were prepared via the sol-gel route. The as-prepared ZnO nanoparticles showed nanocrystallites in rod-like shapes with a non-uniform hexagonal cross-section and diameter varying from 40 to 75 nm. PS/ZnO nanocomposites with ZnO nanoparticles content ranging from 0–3 wt% are prepared via the common casting method. Even dispersion for ZnO nanoparticles within as-prepared PS/ZnO nanocomposites was verified through SEM/EDX measurements. Thermal degradation of the samples was checked by using the thermogravimetric (TG) analysis and differential scanning calorimetry (DSC) under non-isothermal conditions and a constant heating rate of 10 °C min. The thermal stability of the nanocomposite is elevated compared to that of pristine PS due to the addition of the ZnO nanoparticles. The homogeneity of the PS/ZnO nanocomposites is verified by systematic increases in thermal degradation with increasing ZnO content. The characterization degradation temperatures at different weight loss percentages of ZnO nanoparticles increase at high ZnO wt%. Static activation energy of decomposing is based on TGA data. Activation energies showed some enhancement after the addition of ZnO nanorods into the PS matrix. Enhancing the thermal stability of PS with ZnO addition within the investigated ZnO concentration range is verified by TG, DSC results.