Volatile organic compounds (VOCs) have vital implications for secondary pollutants, atmospheric oxidation and human health. Ambient VOCs were investigated using an online system, gas chromatography-mass spectrometry/flame ionization detector (GC-MS/FID), at a suburban site in Xianghe in the North China Plain from 6 November 2017 to 29 January 2018. Positive matrix factorization (PMF) receptor model was applied to identify the major VOC contributing sources. Four-step health risk assessment method was used to estimate risks of all risk-posing VOC species. A total of 101 VOCs were quantified, and the mean concentration of total VOCs was 61.04 ± 65.18 ppbv. The VOCs were dominated by alkanes (38.76%), followed by alkenes, aromatics, halocarbons, OVOCs, acetylene and acetonitrile. The results of PMF revealed that vehicle exhaust, industrial emissions, liquefied petroleum gas & natural gas, solvent utilization and secondary and long-lived species contributed 31.0%, 26.4%, 18.6%, 13.6% and 10.4%, respectively, to the total VOCs. Pollutant-specific and source-specific noncarcinogenic and carcinogenic risk estimates were conducted, which showed that acrolein and vehicle exhaust had evident noncarcinogenic risks of 4.9 and 0.9, respectively. The carcinogenic risks of specific species (1,3-butadiene, acetaldehyde, benzene, chloroform and 1,2-dichloroethane) and identified sources were above the United States Environmental Protection Agency (USEPA) acceptable level (1.0 × 10) but below the tolerable risk level (1.0 × 10). Vehicle exhaust was the largest contributor (56.2%) to noncarcinogenic risk, but solvent utilization (32.6%) to carcinogenic risk. Moreover, with the evolution of pollution levels, almost all VOC species, contributions of alkenes, aromatics, solvent utilization and vehicle exhaust, and pollutant-specific and source-specific risks increased continuously and noticeably. Collectively, our findings unraveled the importance of alkenes, aromatics, solvent utilization and vehicle exhaust in the evolution of pollution levels. Future studies should consider targeting these VOC groups and sources when focusing on effective reduction strategies and assessing public health risks.