Rational structure design of 3D hosts is one of the most promising strategies to achieve uniform Li deposition and inhibit the uncontrolled growth of Li dendrites. Herein, a 3D-C_TPA skeleton with lithiophobic–lithiophilic properties was used for the fabrication of a 3D composite Li anode (3D-C_TPA@Li) by electrodeposition. The resulting 3D-C_TPA@Li symmetric cell showed a long lifespan of 2000 h at 1 mA cm⁻² for 1 mA h cm⁻². Additionally, the 3D-C_TPA@Li/LiFePO₄ full cell exhibited long cyclic stability with 86.6% capacity retention after 500 cycles at 0.5C. The good electrochemical performance of the 3D-C_TPA@Li anode can be attributed to the unique features of the 3D-C_TPA skeleton, which resulted in dominant Li(110) facets for enhanced electrochemical kinetics. This was supported by XPS results, which indicated the formation of an inorganic-rich SEI layer on the surface of the 3D-C_TPA@Li anode. The robust SEI layer with heterogenous electronic insulated/ionic conductive (Li₃N/LiF) properties could effectively inhibit the reduction of Li⁺ and the electrolyte on the surface of the 3D-C_TPA@Li anode, as well as serve as an “ionic sieve” to realize uniform and fast Li⁺ transport through the interface. Consequently, metallic Li preferentially nucleated/grew inside the 3D-C_TPA pore spaces with bottom-up Li deposition.