Volatile organic compounds (VOCs) are ubiquitous environmental pollutants and have been implicated in adverse health outcomes. In this study, concentrations of 11 VOC metabolites (mVOCs) and three oxidative stress biomarkers (8-oxo-7,8-dihydro-2'-deoxyguanosine, 8-oxo-7,8-dihydro-guanosine, and dityrosine) were determined in 205 urine samples collected from 12 cities across mainland China. Urinary ∑mVOC concentrations ranged from 498 to 1660 ng/mL, with a geometric mean (GM) value of 1070 ng/mL. The factorial analysis revealed that cooking, solvents, and vehicle emissions were the three primary sources of VOC exposure. A significant regional variation was clearly found in ∑mVOC concentrations across four regions in China, with high urine VOC concentrations found in North and South China (GM: 1450 and 1340 ng/mL). The multiple linear regression model revealed that most mVOCs were significantly positively correlated with three oxidative stress markers (β range: 0.06-0.22). Mixture effect regression showed that isoprene, crotonaldehyde, acrolein, and benzene were the strongest contributors to oxidative stress. Approximately 80% of the participants have HQ values greater than 1.0 for 1,3-butadiene and benzene, suggesting that their exposure doses were close to potential adverse health effects. Our findings provide comprehensive information on human exposure and potential health risks of VOCs in China.