The thermal management of electronics has gained significant attention, with loop heat pipes (LHPs) emerging as an attractive solution for heat dissipation. The heat transfer performance of LHPs is influenced by the heat and mass transfer processes within the wick. However, designing the pore diameter of the wick is challenging due to the different requirements of flow resistance and capillary force. Specifically, the working fluid needs large pores to reduce resistance, while the liquid suction requires small pores to provide a large capillary force. To address this issue, we drew inspiration from the stomatal array of natural leaves used for transpiration and developed an alumina ceramic bionic wick with finger-like pores using the phase-inversion tape casting method. The finger-like pores in the wick resemble the straight hole structure of stomata, which increases the gas−liquid interface area within the wick. This design allows for timely discharge of water vapor generated by boiling, thereby reducing mass transfer resistance. Additionally, numerous micrometer-sized small pores surrounding the finger-like pores provide sufficient capillary force to replenish liquid for the gas−liquid evaporation interface. Experimental results demonstrate that the introduction of finger-like pores in the wick increases gas and water permeabilities by 2.4 and 5.2 times, respectively. Furthermore, the superior heat and mass transfer performance of the bionic wick was demonstrated with an LHP. This work effectively addresses the conflicting demands of capillary force and flow resistance, enhancing the heat transfer performance of LHPs, which holds great promise for addressing heat dissipation challenges in high power density electronic chips and has potential applications in aviation, aerospace, and microelectronics for efficient thermal management.