This paper proposes a risk assessment method combining event tree analysis and numerical simulation, to assess the risks of truck-to-ship bunkering operations for methanol-fueled ships and enhance the safety level of methanol bunkering. Risk factors for methanol bunkering operations were identified based on ship layout, bunkering system, and operational procedures. An event tree model for methanol leakage was established considering influencing factors such as ignition conditions, leakage source location, and fire protection system response. The occurrence probabilities of different scenarios were calculated using typical failure data. On this basis, the three-dimensional computational fluid dynamics (CFD) tool FLACS was used to simulate the distribution of flammable hazard zones and toxic hazard zones following methanol leakage. Individual risk values were calculated according to the acceptable individual risk criterion. The results show that the individual risk of truck-to-ship bunkering operations for methanol-fueled ships is at an unacceptable level. It is recommended that based on quantitative calculation results, the restricted area for bunkering operations be delineated along the vessel's length and breadth directions according to the flammability limits, and a warning zone be established with the methanol tanker as the center and the toxic concentration limit as the radius. The research findings can provide input for the development of bunkering operation manuals for methanol-fueled ships.