Air pollution (PM2.5) has been associated with cardiovascular disease (CVD) globally and with early atherosclerosis surrogate markers in modernized China. A sizeable number of Chinese have migrated overseas, with an increase in their vulnerability to CVD. To evaluate the impact of PM2.5 air pollution on atherogenesis in native vs. overseas Chinese, we recruited 756 asymptomatic native Chinese and 507 age- and gender-matched overseas Chinese from Sydney and San Francisco. Their cardiovascular profiles were evaluated. PM2.5 was derived from remote sensing technology; atherosclerosis surrogate markers, flow-mediated dilation (FMD) and carotid intima-media thickness (IMT) were measured by ultrasound. The native Chinese had a higher proportion of smokers as well as higher blood pressure, glucose, metabolic syndrome and PM2.5 exposure (p < 0.001), but lower lipids and folate than the overseas Chinese (p < 0.0001). Carotid IMT was lower in the native Chinese (p < 0.0001), but the other vascular parameters were similar. A multivariate regression revealed that FMD in the native Chinese was related to the male gender, age and location; in the overseas Chinese, it was related to age, but not to PM2.5. Carotid IMT in the native Chinese was related to PM2.5, independent of atherosclerotic risk factors and location (R2 = 0.384, F = 34.5, p < 0.0001) whereas in the overseas Chinese, IMT was related to the male gender and age, but not to PM2.5 or overseas location (R2 = 0.282, F = 19.7, p < 0.0001). PM2.5 had a greater impact on atherogenesis in the native Chinese, independent of traditional risk factors, with implications for preventive strategies.