Surface ozone (O3) pollution is an emerging environmental abiotic stress that poses substantial risks to crop yield losses and food security worldwide, and especially in China. However, the O3-induced detrimental effects on double-season rice have rarely been investigated at large scales and over relatively long temporal spans. In this study, we estimated the crop production reductions and associated economic losses for double-season rice across southern China during 2013–2019, using a high spatial resolution surface ozone reanalysis dataset and rice distribution maps, and county-level production data, in combination with a locally derived exposure-response function for rice. Results show that AOT40 (cumulative hourly O3 exposure above 40 ppb) presented generally increasing trends over growing seasons in 2013–2019, spanning from 4.0 to 7.1 ppm h and 6.1 to 10.5 ppm h for double-early rice and double-late rice, respectively. Moreover, O3-induced relative yield losses ranged from 4.0% to 6.6% for double-early rice and 6.3% to 11.1% for double-late rice. Over the seven years, ambient O3 exposure resulted in crop production losses of 1951.5 × 104 tons and economic losses of 8,081.03 million USD in total. To combat the O3-induced agricultural risks, measures such as stringent precursors emission reductions and breeding O3-resistant cultivars should be continuously implemented in the future.