One of the major pollutants influencing urban air quality in China is O₃. O₃ is the second most important pollutant affecting air quality in Shijiazhuang, which is the third largest city in the Beijing-Tianjin-Hebei area and the provincial capital of Hebei province. To fully understand the characteristics of O₃ and volatile organic compounds (VOCs), which are O₃ precursors, and the role of VOCs to ozone formation, we measured the hourly concentrations of O₃ and 85 VOCs in Shijiazhuang continuously from January to November 2020, and the concentration characteristics of both together with the chemical reactivity and sources of VOCs were analyzed from a seasonal perspective. The O₃ concentration in Shijiazhuang showed a phenomenon of high summer and low winter, and the VOCs showed a phenomenon of high winter and low spring. In the summer when the O₃ exceedance rate is the highest, the time-domain variation characteristics of O₃ were analyzed by wavelet analysis model, and the main periods controlling the O₃ concentration variation in Shijiazhuang in summer 2020 were 52 days, 32 days, 19 days and 12 days. The maximum incremental reactivity (MIR) and propylene equivalence method indicated ethene, propylene and 1-pentene were common substances in the top five species of each season. The T/B, Iso-p/N-p, Iso-p/E, N-p/E, and positive matrix factorization (PMF) model showed that industrial source (18.62%–22.03%) and vehicle emission (13.20%–17.69%) were the major VOCs sources in Shijiazhuang. Therefore, to control the O₃ concentration in Shijiazhuang, it is necessary to decrease alkenes emissions as well as VOCs from industrial source and vehicle emission.