Large cities in China are experiencing severe ambient air pollution. Although China accounts for more than 45% of new cases of nasopharyngeal carcinoma worldwide in 2018, few studies have examined the association between ambient air pollution and the high nasopharyngeal carcinoma (NPC) incidence in China. Thus, we aim to investigate whether exposure to ambient air pollution (including nitrogen dioxide, sulfur dioxide, and PM10) would significantly affect NPC incidence in large Chinese cities. We collected panel data of ten Chinese provincial cities about local NPC incidence, air pollution level, meteorology, and city profiles during 2006 to 2013 to construct a two-way fixed-effects model to explore the association between ambient air pollution and NPC incidence, as well as possible regional and gender differences behind the association. We found that NO2 had the strongest association with NPC incidence, and the relative risks were 2.2995 (95% CI, 1.2567–4.2075) for males and 1.3010 (95% CI, 0.8212–2.0620) for females, respectively. Under cumulative exposure, it was still NO2 that had the strongest association with NPC incidence, with a relative risk of 1.8836 (95% CI, 1.2416–2.8577), compared to 1.0857 (95% CI, 0.9474–1.2450) and 1.0547 (95% CI, 0.8790–1.2663) for SO2 and PM10, respectively. In addition, males were found more sensitive to ambient air pollution than females. We also found that southern Chinese cities were more sensitive to NO2 than northern cities, which might be related to a higher humidity there. Our study reveals that exposure to ambient air pollutants like SO2, PM10, and particularly NO2, is significantly positively associated with NPC incidence in China.