The registration rate of eco-friendly vehicles, such as hydrogen vehicles, is increasing rapidly, however, few first responders have experienced related accidents. Accident scenarios at hydrogen refueling stations and hydrogen vehicles on a road were investigated, and the relative importance of each scenario was analyzed using AHP analysis. Leakage, jet flame, and explosion that occurred inside and outside the hydrogen refueling station were reviewed, and the hydrogen gas explosion in the compartment showed the highest importance value. In case of the hydrogen vehicle, traffic accident statistics and actual accidents were used. It was analyzed that the hydrogen vessel explosion on the road due to the failure of TPRD and the leakage in the underground parking area were difficult to respond. The developed accident scenarios are expected to be used for first responder training.