Background Previous studies indicated that exposure to ambient fine particulate matter (PM 2.5 ) could increase the risk of metabolic syndrome (MetS). However, the specific impact of PM 2.5 chemical components remains uncertain. Methods A national cross-sectional study of 12,846 Chinese middle-aged and older adults was conducted. Satellite-based spatiotemporal models were employed to determine the 3-year average PM 2.5 components exposure, including sulfates (SO 4 2− ), nitrates (NO 3 − ), ammonia (NH 4 + ), black carbon (BC), and organic matter (OM). Generalized linear models were used to investigate the associations of PM 2.5 components with MetS and the components of MetS, and restricted cubic splines curves were used to establish the exposure-response relationships between PM 2.5 components with MetS, as well as the components of MetS. Results MetS risk increased by 35.1, 33.5, 33.6, 31.2, 32.4, and 31.4% for every inter-quartile range rise in PM 2.5 , SO 4 2− , NO 3 − , NH 4 + , OM and BC, respectively. For MetS components, PM 2.5 chemical components were associated with evaluated risks of central obesity, high blood pressure (high-BP), high fasting glucose (high-FBG), and low high-density lipoprotein cholesterol (low-HDL). Conclusion This study indicated that exposure to PM 2.5 components is related to increased risk of MetS and its components, including central obesity, high-BP, high-FBG, and low-HDL. Moreover, we found that the adverse effect of PM 2.5 chemical components on MetS was more sensitive to people who were single, divorced, or widowed than married people.