Aluminum nitride (AlN), noted for its excellent thermal conductivity and exceptional electrical insulation, presents a promising alternative to traditional ceramic particles in thermal interface materials (TIMs). However, its broader adoption in practical applications is limited by performance degradation due to the vulnerability of its crystal structure to ubiquitous moisture. This study introduces a dual solution, utilizing a mechanochemical method to design a dense outer layer of Galinstan liquid metal (LM) that simultaneously enhances AlN's resistance to hydrolysis and improves its thermal performance in TIM applications. The high surface free energy of the LM layer imparts hydrophobic properties to the AlN surface and, combined with outer metal oxides, forms a dual-layer protective barrier that prevents water penetration, significantly enhancing the TIM's long-term stability in high-humidity conditions. Additionally, the LM layer at the interface improves the thixotropic properties of the TIM and enhances interfacial heat transport through the bridging effect of the LM, resulting in improved rheological mobility and thermal conductivity of the composite material. This win-win surface modification strategy opens opportunities for the practical and durable application of AlN in widespread electronic thermal management.