In the fall of 2007 concurrent air sampling field measurements were conducted for the first time in Guangzhou (at Wan Qing Sha (WQS)) and Hong Kong (at Tung Chung (TC)), two cities in the rapidly developing Pearl River Delta region of China that are only 62 km apart. This region is known to suffer from poor air quality, especially during the autumn and winter months, when the prevailing meteorological conditions bring an outflow of continental air to the region. An interesting multiday O3 pollution event (daily maximum O3 > 122 ppbv) was captured during 9–17 November at WQS, while only one O3 episode day (10 November) was observed at TC during this time. The mean O3 mixing ratios at TC and WQS during the episode were 38 ± 3 (mean ± 95% confidence interval) and 51 ± 7 ppbv, respectively, with a mean difference of 13 ppbv and a maximum hourly difference of 150 ppbv. We further divided this event into two periods: 9–11 November as Period 1 and 12–17 November as Period 2. The mixing ratios of O3 and its precursors (NOx and CO) showed significant differences between the two periods at TC. By contrast, no obvious difference was found at WQS, indicating that different air masses arrived at TC for the two periods, as opposed to similar air masses at WQS for both periods. The analysis of VOC ratios and their relationship with O3 revealed strong O3 production at WQS during Period 2, in contrast to relatively weak photochemical O3 formation at TC. The weather conditions implied regional transport of O3 pollution during Period 1 at both sites. Furthermore, a comprehensive air quality model system (Weather Research and Forecasting–Community Multiscale Air Quality model (WRF-CMAQ)) was used to simulate this O3 pollution event. The model system generally reproduced the variations of weather conditions, simulated well the continuous high O3 episode event at WQS, and captured fairly well the elevated O3 mixing ratios in Period 1 and low O3 levels in Period 2 at TC. The modeled surface O3 distributions and flow structures clearly illustrated the occurrence of O3 formation and the impact of regional transport on O3 levels in Period 1 in the Pearl River Delta. Further analysis of O3 formation indicated that horizontal transport was the main contributor to the O3 increase at TC during Period 1, while at WQS O3 levels were dominated by photochemical production during both periods. The low O3 levels at TC during Period 2 were attributable to lower temperatures and the arrival of fresh maritime air masses brought in by strong easterly winds. This study highlights how contrasting precursor concentrations and photochemical conditions can occur over a very small distance, and it provides a rare opportunity to better understand ozone production and precursor source origins on a finer scale in this region.