Loop heat pipe (LHP) is known as a two-phase heat transfer device that utilizes the evaporation and condensation of an operating fluid to transfer heat. At the LHP low operating temperatures, heat leakage induced by saturated temperature differences between the evaporator and compensation chamber is more serious than at high operating temperatures, due to inherent thermophysical properties of the operating liquid. The serious heat leakage at the low operating temperature not only causes high liquid subcooling requirement but also leads to high total temperature difference and degraded heat transfer performance. In this paper, research efforts are placed on reducing the heat leakage by introducing a multilayer wick structure into the LHP. Based on the previous research results of LHP non-metallic wick structures, the multilayer wick LHP combines advantages of both metallic and non-metallic wick structures, retains good heat conduction from the evaporator case to the liquid/vapor interface and inhibits the reverse heat transfer from the interface to compensation chamber. By demonstrating the concept on a methanol LHP, experimental results exhibit a significant enhancement in reducing heat leakage and the total heat transfer resistance.