AbstractThe deployment of Li‐garnet Li₇La₃Zr₂O₁₂ (LLZO) solid‐state electrolytes in solid‐state batteries is severely hampered by their poor wettability with metallic Li. In this work, Sb is presented as a compelling interfacial layer allowing superior wetting of Li onto a LLZO surface, resulting in a remarkably low Li/LLZO interfacial resistance of 4.1(1) Ω cm². An atomistic insight into Sb‐coated LLZO interface using soft and hard X‐ray photoelectron spectroscopy and focused ion beam time‐of‐flight secondary ion mass spectrometry shows the formation of a Li‐Sb alloy as an interlayer. It is determined that the Li/Sb‐coated LLZO/Li symmetrical cells exhibit a high critical current density of up to 0.64 mA cm⁻² and low overpotentials of 40–50 mV at a current density of 0.2 mA cm⁻² without applying external pressure. The electrochemical performance of Sb coated‐LLZO pellets is also assessed with an intercalation‐type V₂O₅ cathode. Li/Sb‐coated‐LLZO/V₂O₅ full cells deliver stable capacities of around 0.45 mAh cm⁻², with a peak current density of 0.3 mA cm⁻².