Given the deteriorating situation of ambient ozone (O₃) pollution in some areas of China, understanding the mechanisms driving O₃ formation is essential for formulating effective control measures. This study examines O₃ formation mechanisms and RO_x (OH, HO_2, and RO₂) radical cycling driven by photochemical processes in Bozhou, located at the junction of Jiangsu–Anhui–Shandong–Henan (JASH), a region heavily affected by O₃ pollution, by applying a zero-dimensional box model (Framework for 0-Dimensional Atmospheric Modeling, F0AM) coupled with the Master Chemical Mechanism (MCM v3.3.1) and Positive Matrix Factorization (PMF 5.0) to characterize O₃ pollution, identify volatile organic compound (VOC) sources, and quantify radical budgets during pollution episodes. The results show that O₃ episodes in Bozhou mainly occurred in June under conditions of high temperature and low wind speed. Oxygenated volatile organic compounds (OVOCs), alkanes, and halocarbons were the dominant VOCs groups. The CH₃O₂ + NO reaction accounted for 24.3% of O₃ production, while photolysis contributed 68.7% of its removal. Elevated VOCs concentrations in Bozhou were largely maintained by anthropogenic sources such as vehicle exhaust, solvent utilization, and gasoline evaporation, which collectively enhanced O₃ production. The findings indicate that O₃ formation in the region is primarily regulated by NO_x availability. Therefore, emission reductions targeting NO_x, along with selective control of OVOCs and alkenes, would be the most effective strategies for lowering O₃ levels. Model simulations further highlight Bozhou’s strong atmospheric oxidation capacity, with OVOC photolysis identified as the dominant contributor to RO_x generation, accounting for 33% of the total. Diurnal patterns were evident: NO_x-related reactions dominated radical sinks in the morning, while HO₂ + RO₂ reactions accounted for 28.5% in the afternoon. By clarifying the mechanisms of O₃ formation in Bozhou, this study provides a scientific basis for designing ozone control strategies across the JASH junction region. In addition, ethanol was not directly measured in this study; given its potential to generate acetaldehyde and affect local O₃ formation, its possible contribution introduces additional uncertainty that warrants further investigation.