Lithium (Li) is a metallic element possessing the most negative electrode potential and the lowest electrochemical equivalent, which make it one of the key materials for the development of the next-generation Li batteries with high specific energy. However, the heterogeneous deposition, volume expansion, solid-electrolyte interphase (SEI) fracture, and high reactivity of metallic Li make its commercialized development difficult. Herein, a novel polyaniline (PANI) decorated three-dimensional (3D) copper mesh (3DCMP) skeleton for a Li metal anode is proposed, which was prepared by in situ polymerizing aniline on the surface of a copper mesh (3DCM). The lithiophilic PANI micro-sheets could induce ordered Li deposition on the mesh and facilitate the formation of a more available SEI film, which could effectively alleviate the formation of Li dendrites and highly promote the utilization of Li during long-term cycling. The symmetrical-cell displayed an excellent Li plating/stripping performance, in which it maintained an overpotential of less than 20 mV at a current density of 2 mA cm⁻² over 4000 h. Furthermore, the full-cell coupled with the LiFePO₄ cathode exhibited a high capacity retention of 84.8% at 4C after 550 cycles and when coupled with the rGO/S cathode exhibited a capacity retention of 94.4% at 1C after 100 cycles. Hence, it demonstrates a promising potential to be applied in large-scale manufacturing.