Liquid hydrogen has been studied for use in vehicles. However, during the charging process, liquid hydrogen is lost as gas. Therefore, it is necessary to estimate and reduce this loss and simulate the charging process. In this study, the initial charging process of a vehicle liquid hydrogen tank under room temperature and atmospheric pressure conditions was numerically investigated. A transient thermal-fluid simulation with a phase-change model was performed to analyze variations in the volume, pressure, mass flow rate, and temperature. The results showed that the process could be divided into three stages. In the first stage, liquid hydrogen was actively vaporized at the inner wall surface of the storage tank. The pressure increased rapidly, and liquid droplets were discharged into the vent pipe during the second stage. In the third stage, the mass flow rates of liquid and hydrogen gas at the outlet showed significant fluctuations, owing to complex momentum generated by the evaporation and charging flow. The temperatures of the inner and outer walls, and insulation layer, decreased significantly slower than that of the gas region because of its high heat capacity and insulation effect. The optimal structure should be further studied because the vortex, stagnation, and non-uniform cooling of the wall occurred near the inlet and outlet pipes.