Benzene exposure affects gasoline station personnel, and prior studies have shown that working at gasoline stations has a greater effect on neurological symptoms. This study aims to examine the risk of benzene exposure and evaluate workers’ knowledge and preventive practices regarding benzene at gasoline stations in Northeastern Thailand. A questionnaire was utilized to collect data on general knowledge and preventive practices from 82 employees across 57 gasoline stations. Twelve specific benzene samples were collected, with two samples obtained from each of six gasoline stations: one from the gasoline refueling zone and one from the office area. Sampling adhered to the NIOSH-1501 standard using personal pumps. A gas chromatograph (GC) equipped with a flame ionization detector (FID) was employed to detect benzene. Descriptive statistical analysis was conducted to determine frequency, percentage, mean, maximum, and minimum values. Our findings revealed that benzene concentrations in all samples were below the detection threshold (0.001 mg/kg) during the 8-hour work shift. Strikingly, despite this low measured exposure and acceptable non-cancer risk levels, every work group was still classified as having a significant cancer risk according to the risk assessment models. The study also indicated that 50.0% of workers had a moderate understanding of benzene, whereas 45.1% had a low level of knowledge. Moreover, self-protective measures were inadequate, with workers neglecting to wear protective gloves while handling benzene, delaying gasoline removal until task completion, and consuming food and beverages in the workplace. Our findings provide more evidence about the health risk associated with benzene exposure among gasoline station workers. Therefore, organizations and relevant agencies must prioritize improving workers’ understanding of safe chemical management to ensure proper handling and minimize exposure to carcinogenic substances that may increase cancer risk.