To overcome the two-phase flow instability of traditional boiling heat dissipation technologies, a porous wick was used for liquid-vapor isolation, achieving efficient and stable boiling heat dissipation. A pump-assisted capillary phase-change loop with methanol as the working medium was established to study the effect of liquid-vapor pressure difference and heating power on its start-up and steady-state characteristics. The results indicated that the evaporator undergoes four heat transfer modes, including flooded, partially flooded, thin-film evaporation, and overheating. The thin-film evaporation mode was the most efficient with the shortest start-up period. In addition, heat transfer modes were determined by the liquid-vapor pressure difference and power. The heat transfer coefficient significantly improved and the thermal resistance was reduced by increasing liquid-vapor pressure as long as it did not exceed 8 kPa. However, when the liquid-vapor pressure exceeded 8 kPa, its influence on the heat transfer coefficient weakened. In addition, a two-dimensional heat transfer mode distribution diagram concerning both liquid-vapor pressure difference and power was drawn after a large number of experiments. During an engineering application, the liquid-vapor pressure difference can be controlled to maintain efficient thin-film evaporation in order to achieve the optimum heat dissipation effect.