Based on our previous research, the composite porous wick with spherical-dendritic powders owns biporous structure and uneven local thermal conductivity. In this paper, a multi-composite porous wick sintered with three different materials and structures of spherical copper, spherical nickel and dendritic nickel is tested. The spherical copper is beneficial to expansion of the evaporation heat transfer area, the dendritic nickel can provide sufficient liquid for evaporation, and the spherical nickel is used to regulate the distribution of spherical-dendritic powders and large pores. Through the evaporation heat transfer experiment, it is found that there are five different types of operating temperature and evaporation mass curves, including continuous and intermittent overshoot, single overshoot, stable operation and temperature losing control. The occurrence of the overshoot is affected by the bubble behavior in the bottom of the porous wick. And two types of the vapor–liquid interface behavior occur in the overshoot operation, in which the porous wick is penetrated by a single bubble or the evaporating interface, respectively. The multi-composite porous wick can reach a maximum heat load of 520 W (the corresponding heat flux is 43.5 W/cm2), and the highest heat transfer coefficient of the open capillary evaporator can reach 2776.1 W/(m2·K), with the lowest total thermal resistance is 0.3089 K/W at 500 W heat load. As a reference using a composite porous wick prepared with spherical copper powder and dendritic nickel powder of the same volume ratio, its maximum heat load is only 210 W (the corresponding heat flux is 17.6 W/cm2). The multi-composite porous wick shows better evaporation heat transfer performance. After the evaporation heat transfer experiment, the oxidized multi-composite porous wick still shows good wettability. It is inferred that a mixed wetting structure is formed inside it due to the composite structure sintered by three kinds of metal powders, which may be beneficial for improving the evaporation heat transfer performance of the multi-composite porous wick. In addition, the conditions such as lower effective thermal conductivity, more uneven local thermal conductivity, and large pores provided by the unchanged spherical nickel powder may also play a role.