As major air pollutants and key precursors of several secondary air pollutants, nitrogen oxide (NOx) emissions are regulated in many countries. However, NOx control increases ozone concentrations when the ozone formation regime is volatile organic compound (VOC) limited. Although many studies have shown that NOx regulation reduces ozone levels over the long term, it is still of concern that NOx regulation increases short-term ozone levels in metropolitan regions, where ozone formation is found to be predominantly VOC-limited. The Pearl River Delta (PRD) in China is such a region. Our modeling sensitivity study shows that while NOx reduction in the PRD region may raise the mean ozone concentration, it can also decrease peak ozone levels. Similar changes are observed in the NOx and ozone data of the PRD regional air quality monitoring network (2006–2012), lending further credence to our results. In the model, this NOx control effect is a result of the complicated spatial and diurnal variations of the ozone formation regime. In most of the PRD region, the formation regime is VOC-limited in the morning and becomes NOx-limited during peak ozone hours. Although some areas are always VOC-limited, their ozone concentrations are relatively low, and the ozone increases caused by NOx reduction generally do not cause higher ozone levels than the region's original ozone maxima. Several control scenarios are simulated to evaluate the effects of various possible control regulations. Our results show that in addition to VOC control, NOx control can be effective for reducing peak ozone concentrations in the PRD region.