Lithium metal is among the most promising anode candidate of the high-energy battery. However, the formed dendrites result in low Coulombic efficiency and serious security issues. Designing lithiophilic sites is one of the effective strategies to control Li deposition. Herein, we propose a three-dimensional lithiophilic N-rich carbon nanofibers with the decoration of ZnO granules as a protective layer for dendrite-free lithium metal anode. Theoretical evaluation indicates the synergistic effects of lithiophilic ZnO and N-containing functional groups enhance the lithium adsorption and trigger the uniform deposition. With the lithiophilic interlayer, lithium deposition overpotential is only ~20, 50, and 74 mV at 1, 3, and 6 mA cm-2, respectively, which are much lower than these without the functional interlayer (~55, 130, and 238 mV). The Coulombic efficiency of lithium stripping and plating is up to ∼98.0% (92.5% for that without interlayer) after 120 cycles at 0.5 mA cm-2. Meanwhile, the Li|LiFePO4 full cell with the superlithiophilic interlayer demonstrates a high capacity retention rate of 99.6% (91.0% for that without interlayer) over 200 cycles at 1 C. The introduction of lithiophilic interphase could provide a convenient strategy and guidance to design the configuration for the practical application of Li metal batteries.