•Positive associations of air pollutants with MetS were found in rural Chinese adults.•Physical activity was negatively associated with MetS in rural Chinese adults.•Air pollutants attenuated the negative association of physical activity with MetS. Long-term exposure to ambient air pollution and physical activity are linked to metabolic syndrome (MetS). However, the joint effect of physical activity and ambient air pollution on MetS remains largely unknown in rural Chinese adult population. In this study, 39 089 individuals were included from the Henan Rural Cohort study that recruited 39 259 individuals at the baseline. Participants' exposure to air pollutants (including particulate matter with an aerodynamic diameter ≤ 1.0 µm (PM1), ≤2.5 µm (PM2.5), or ≤ 10 µm (PM10) and nitrogen dioxide (NO2)) were evaluated by using a spatiotemporal model based on satellites data. Individuals were defined as MetS according to the recommendation of the Joint Interim Societies. Physical activity-metabolic equivalent (MET) was calculated based on the formula of MET coefficient of activity × duration (hour per time) × frequency (times per week). Generalized linear models were used to analyze the individual air pollutant or physical activity and their interaction on MetS. Interaction effects of individual air pollutant and physical activity on MetS were assessed by using Interaction plots which exhibited the estimated effect of physical activity on MetS as a function of individual air pollutant. The prevalence of MetS was 30.8%. The adjusted odd ratio of MetS with a per 5 µg/m3 increase in PM1, PM2.5, PM10, NO2 or a 10 MET (hour/day) of physical activity increment was 1.251(1.199, 1.306), 1.424(1.360, 1.491), 1.228(1.203, 1.254), 1.408(1.363, 1.455) or 0.814(0.796, 0.833). The protective effect of physical activity on MetS was decreased with accompanying air pollutant concentrations increased. The results indicated that long-term exposure to ambient air pollutants related to increased risk of MetS and physical activity attenuated the effects of ambient air pollutants on increased risk for MetS.