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Aim: The rising prevalence of periodontitis imposes substantial burdens on individuals and society. Identifying environmental risk factors for periodontitis may contribute to tackling the global public health burden of it. This study aimed to assess the association between long‐term exposure to PM2.5 and periodontitis in a nationally representative population from China. Materials and Methods: In this multi‐centre cross‐sectional study of 372 communities in 31 provinces of Mainland China, we used data from the Fourth National Oral Health Survey of China in 2015–2016, in combination with high‐resolution gridded concentrations of fine particulate matter (PM2.5). Logistic regression was applied to assess the relationship between long‐term PM2.5 exposure and the risk of periodontitis. In addition, we examined whether the association varied by individual characteristics, and estimated the exposure–response relationship and the risk of damaged tooth in each tooth quadrant. Results: A total of 8391 participants from 96 cities were diagnosed with periodontitis, accounting for 60.04% (8391/13,459) of the participants. For each 10 μg/m3 increment in 1‐, 3‐ and 5‐year average concentrations of PM2.5, the risk of total periodontitis increased by 9.0% (95% confidence interval: 6.0%, 12.0%), 8.0% (6.0, 11·0) and 7.0% (5.0, 10.0), respectively. Mild periodontitis was more strongly associated with PM2.5 exposure than moderate and severe periodontitis. The teeth in the lower anterior, lower posterior or upper anterior are more susceptible to the effect of PM2.5 on the periodontal pocket, calculus and bleeding gums. Conclusions: Long‐term exposure to PM2.5 is significantly associated with an increased risk of periodontitis in the nationally representative Chinese population. Considering the rising prevalence of periodontitis, considerable costs of treatment, and substantially adverse effects on individuals and society, these findings suggest that stricter air quality regulations may help ease the burden of periodontal disease. [ABSTRACT FROM AUTHOR]