The demand for hydrogen, a carbon-neutral fuel, is expected to increase in the coming decades. However, the current storage efficiency of gaseous hydrogen is poor. Liquid organic hydrogen carriers (LOHC), which store hydrogen in liquid form under ambient conditions, show promise for on-site hydrogen refueling stations. Toluene-methylcyclohexane is one of LOHC, it has advantages cost-effect and environmentally to large-scale hydrogen transportation, but it should be evaluated risk assessment based on the chemicals, because there is inherent harm from the properties like toxicity or flammability. Herein, quantitative risk assessment (QRA) results worst-case scenarios, individual risk (IR), and societal risk (SR) for a Methylcyclohexane-based on-site hydrogen refueling station (MHRS) are compared with those a gaseous hydrogen refueling stations (GHRS). The latter is more likely to have explosion-related accidents while the former is more likely to have had fire-related accidents. Both show similarly high societal risks. The rupture of the MCH storage tank poses the most significant risk, but installing a dike reduces by 86%, thereby placing it within acceptable limits. Thus, the key risk factors for future on-site hydrogen refueling stations are identified and insights into mitigating them is offered.