Gasoline is a globally used primary fuel. The submicron particles at gasoline stations have not been extensively investigated. This study aimed to evaluate the exposure concentrations and inhalation risk of submicron particles at a gasoline station. Temporal variations in particle concentrations and size distributions were measured using a real-time system. The effective doses of submicron particles deposited in different organs were analyzed using a computational fluid dynamics model and the value of environmental monitoring (including the size distributions of particles by number). The number concentration (NC) was higher during working hours than that of the background. Submicron particles gathered predominantly at 30.5 nm and 89.8 nm during working time. The effective doses of submicron particles deposited in the olfactory system and lungs were 0.131 × 10−3 and 0.014 mg, respectively, of which 0.026 × 10−3 mg potentially reached the brain. In a female worker with 3 years of exposure, the average daily effective doses in the olfactory system, lungs, and brain were 2.19 × 10−7 mg/kg·d−1, 2.34 × 10−5 mg/kg·d−1, and 4.35 × 10−8 mg/kg·d−1, respectively. These findings indicated that workers at this gasoline station had a high inhalation risk of submicron particles. This study provides baseline data on submicron particles at gasoline stations and a critical basis for investigating disease risk in longitudinal epidemiological studies.