Most existing studies have investigated short-term associations between ozone exposure and acute disease events among children at a daily timescale, which might neglect risk effects happening within several hours after ozone exposure. In this research, we aimed to depict intraday associations between pediatric emergency department visits (PEDVs) and exposure to ozone in order to better detect ultra-short-term effects of ozone exposure on children. We obtained hourly data of all-cause PEDVs, air pollutants, and meteorological factors in Shenzhen and Guangzhou, China, 2015-2018. We applied time-stratified case-crossover design and conditional logistic regression models to estimate odds ratios per 10-μg/m3 rise of ozone concentrations at various exposure periods (e.g., 0-3, 4-6, 7-12, 13-24, 25-48, and 49-72h) prior to PEDVs, controlling for hourly relative humidity and temperature. Subgroup analyses divided by gender, age, and season were undertaken to identify the potential susceptible population and period. A total of 358,285 cases of PEDVs were included in two cities, and hourly average concentration of ozone was 45.5μg/m3 in Guangzhou and 58.9μg/m3 in Shenzhen, respectively. Increased risks of PEDVs occurred within a few hours (0-3h) after exposure to ozone and remained up to 48h. Population risks for PEDVs increased by 0.8% (95% confidence interval, 0.6 to 1.0) in Shenzhen and 0.7% (0.5 to 0.9) in Guangzhou for a 10-μg/m3 increase in ozone concentrations at lag 4-6h and lag 7-12h, respectively. These findings were robust to co-exposure adjustments in our sensitivity analyses. Significantly greater ozone-associated risks were consistently observed during cold months (October to March of the following year) in both cities, while we did not identify evidence for effect modification of children's age and gender. This study provided novel evidence for increased risks of acute disease events among children within several hours after ozone exposure, highlighting the significant implications for policymakers to establish hourly air quality standards for better protecting children's health.