AbstractFor its high theoretical capacity and low redox potential, Li metal is considered to be one of the most promising anode materials for next‐generation batteries. However, practical application of a Li‐metal anode is impeded by Li dendrites, which are generated during the cycling of Li plating/stripping, leading to safety issues. Researchers attempt to solve this problem by spatially confining the Li plating. Yet, the effective directing of Li deposition into the confined space is challenging. Here, an interlayer is constructed between a graphitic carbon nitrite layer (g‐C3N4) and carbon cloth (CC), enabling site‐directed dendrite‐free Li plating. The g‐C3N4/CC as an anode scaffold enables extraordinary cycling stability for over 1500 h with a small overpotential of ≈80 mV at 2 mA cm−2. Furthermore, prominent battery performance is also demonstrated in a full cell (Li/g‐C3N4/CC as anode and LiCoO2 as cathode) with high Coulombic efficiency of 99.4% over 300 cycles.