Aluminum Nitride ceramic, renowned for its exceptional thermal conductivity, has found extensive applications in power electronics, where surface roughness serves as a critical parameter for its performance. This paper proposed the friction-enhanced chemical polishing to address the conflict between efficiency and surface quality. The Gibbs free energy was calculated through First-Principle method to verify the reactivity of AlN in water environment. Polishing experiment results show that the surface roughness R a reach 8.523 nm and material removal rate reach 3.3198 μm/h after 90 min’s polishing. Comparison experiments were conducted to demonstrate the better performance of the friction-enhanced chemical polishing. Finally, the molecule dynamic was employed to reveal the material removal mechanism.