The "14th Five-Year Plan" period is the key stage for southern Hebei cities (Shijiazhuang, Xingtai, and Handan) to be removed from the bottom ten of the Air Quality Composite Index. The hourly ozone (O3) data of 15 country-controlled monitoring stations in the southern cities of Hebei Province from April to October 2020, hourly data of three volatile organic compound (VOCs) supersites, and the meteorological data of the same period were used for analysis, combined with the spatiotemporal succession, O3 formation potential (OFP), backward trajectory modeling, and spatial statistical modeling. The results showed the following:firstly, the temporal variations in O3 in southern cities of Hebei Province from April to October presented an inverted "U" shape, and the spatial distribution was high in the south and low in the north. O3 pollution was the most serious in June, with Xingtai (233.8 μg·m-3)>Handan (225.2 μg·m-3)>Shijiazhuang (224.8 μg·m-3). O3 was positively correlated with temperature and wind speed and negatively correlated with humidity and VOCs; furthermore, the ρ(TVOC) from April to October followed the order of Xingtai (274 μg·m-3)>Shijiazhuang (266 μg·m-3)>Handan (218 μg·m-3). The total OFP of alkenes and aromatics accounted for more than half; moreover, the trajectory of O3 pollution in southern cities of Hebei Province showed spatial directionality and relevance. The highest mass concentration of O3 (198.92 μg·m-3) was in the trajectory from Shijiazhuang to Xingtai, and the highest frequency of O3 pollution was in the trajectory from Handan to Xingtai. Moreover, the transmission contributions of O3from Xingtai to Shijiazhuang agglomerations were high (27.39%), and Handan played a significant role in the transmission contribution of O3 to Xingtai (32.76%).