Rationally designing a current collector that can maintain low lithium (Li) porosity and smooth morphology while enduring high‐loading Li deposition is crucial for realizing the high energy density of Li metal batteries, but it is still challengeable. Herein, a Li2ZnCu3 alloy‐modified Cu foil is reported as a stable current collector to fulfill the stable high‐loading Li deposition. Benefiting from the in‐situ alloying, the generated numerous Li2ZnCu3@Cu heterojunctions induce a homogeneous Li nucleation and dense growth even at an ultrahigh capacity of 12 mAh cm‐2. Such a spatial structure endows the overall Li2ZnCu3@Cu electrode with the manipulated steric hindrance and outmost surface electric potential to suppress the side reactions during Li stripping and plating. The resultant Li||Li2ZnCu3@Cu asymmetric cell preserves an ultrahigh average Coulombic efficiency of 99.2% at 3 mA cm‐2/6 mAh cm‐2 over 200 cycles. Moreover, the Li‐Li2ZnCu3@Cu||LiFePO4 cell maintains a cycling stability of 87.5% after 300 cycles. After coupling with the LiCoO2 cathode (4 mAh cm‐2), the cell exhibits a high energy density of 407.4 Wh kg‐1 with remarkable cycling reversibility at an N/P ratio of 3. All these findings present a doable way to realize the high‐capacity, dendrite‐free, and dense Li deposition for high‐performance Li metal batteries.