At gas stations, fuel vapors are released into the atmosphere from storage tanks through vent pipes. Little is known about when releases occur, their magnitude, and their potential health consequences. Our goals were to quantify vent pipe releases and examine exceedance of short-term exposure limits to benzene around gas stations. At two US gas stations, we measured volumetric vent pipe flow rates and pressure in the storage tank headspace at high temporal resolution for approximately three weeks. Based on the measured vent emission and meteorological data, we performed air dispersion modeling to obtain hourly atmospheric benzene levels. For the two gas stations, average vent emission factors were 0.17 and 0.21 kg of gasoline per 1000 L dispensed. Modeling suggests that at one gas station, a 1-hour Reference Exposure Level (REL) for benzene for the general population (8 ppb) was exceeded only closer than 50 m from the station's center. At the other gas station, the REL was exceeded on two different days and up to 160 m from the center, likely due to non-compliant bulk fuel deliveries. A minimum risk level for intermediate duration (>14–364 days) benzene exposure (6 ppb) was exceeded at the elevation of the vent pipe opening up to 7 and 8 m from the two gas stations. Recorded vent emission factors were >10 times higher than estimates used to derive setback distances for gas stations. Setback distances should be revisited to address temporal variability and pollution controls in vent emissions.