In order to investigate the seasonal variation in chemical characteristics of VOCs in the urban and suburban areas of southwest China, we used SUMMA canister sampling in Jinghong city from October 2016 to June 2017. Forty-eight VOC species concentrations were analyzed using atmospheric preconcentration gas chromatography–mass spectrometry (GC–MS), Then, regional VOC pollution characteristics, ozone formation potentials (OFP), source identity, and health risk assessments were studied. The results showed that the average concentration of total mass was 144.34 μg·m−3 in the urban area and 47.81 μg·m−3 in the suburban area. Alkanes accounted for the highest proportion of VOC groups at 38.11%, followed by olefins (36.60%) and aromatic hydrocarbons (25.28%). Propane and isoprene were the species with the highest mass concentrations in urban and suburban sampling sites. The calculation of OFP showed that the contributions of olefins and aromatic hydrocarbons were higher than those of alkanes. Through the ratio of specific species, the VOCs were mainly affected by motor vehicle exhaust emissions, fuel volatilization, vegetation emissions, and biomass combustion. Combined with the analysis of the backward trajectory model, biomass burning activities in Myanmar influenced the concentration of VOCs in Jinghong. Health risk assessments have shown that the noncarcinogenic risk and hazard index of atmospheric VOCs in Jinghong were low (less than 1). However, the value of the benzene cancer risk to the human body was higher than the safety threshold of 1 × 10−6, showing that benzene has carcinogenic risk. This study provides effective support for local governments formulating air pollution control policies.