In recent years, ozone pollution has emerged as a significant factor affecting air quality alongside PM2.5, driven by rapid economic development. According to national data, O3 pollution poses severe challenges to air quality management in China. This study investigates the characteristics and sources of volatile organic compounds (VOCs) in the atmosphere of Kaifeng City using the Atmospheric Environment VOCs Automatic Online Monitoring System throughout 2022. Seasonal VOC composition was analyzed, and the ozone formation potential (OFP) was assessed using the ozone generation potential coefficient model and orthogonal matrix factorization. Results indicate that VOC concentrations in Kaifeng follow a pattern of accumulation, consumption, and reaccumulation during typical ozone pollution events. Oxygenated VOCs (OVOCs) dominate concentrations across all stages, followed by alkanes, olefins, aromatics, and halogenated hydrocarbons, while alkynes and organic sulfur compounds remain low. Key VOC sources include solvent usage, fossil and biomass fuel combustion, background pollutants, and traffic emissions. The tropospheric ozone formation potential (TOFP) during the rising, sustained, and dissipating phases of pollution is 182.83 μg·m⁻³, 146.31 μg·m⁻³, and 182.11 μg·m⁻³, respectively. OVOCs, olefins, aromatics, and alkanes are the primary contributors to ozone formation. During the rising phase, industrial emissions and background pollutants are predominant sources, followed by mobile sources and solvent usage. Biomass and fossil fuel combustion dominate during the sustained phase, while mobile sources prevail during the dissipating phase. Effective control of these sources during specific pollution stages is critical to mitigating high ozone levels. This study provides insights into Kaifeng’s VOC pollution characteristics and sources, offering valuable guidance for VOC emission control, ozone pollution mitigation, and public health protection.