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This study evaluates the potential of recycling polystyrene (PS) plastic wastes via a fixed bed (batch) slow pyrolysis reactor. The novelty lies in examining the reactor design, conversion parameters, and reaction kinetics to improve the process yield, activation energy, and chemical composition. PS samples were pyrolyzed at 475–575 °C for 30 min under 10–15 psi. Process yield and product attributes were evaluated using different methods to understand PS thermal degradation characteristics better. The results show that PS decomposition started within 2 min from all temperatures, and the total decomposition point of 97% at 475 °C at approximately 5 min. Additionally, analytical results indicate that the average necessary activation energy is 191 kJ/mol. Pyrolysis oil from PS was characterized by gas chromatography–mass spectrometry. The results show that styrene was produced 57–60% from all leading oil compounds (i.e., 2,4-diphenyl-1-butene, 2,4,6-triphenyl-1-hexene, and toluene), and 475 °C has the major average of conversion effectiveness of 91.3%. The results show that the reactor temperature remains the main conversion parameter to achieve the high process yield for oil production from PS. It is concluded that pyrolysis provides a sustainable pathway for PS waste recycling and conversion to value-added products, such as resins and polymers. The proposed method and analytical results are compared with earlier studies to identify directions for future studies.