All‐solid‐state batteries (ASSB) require stable and safe lithium (Li) metal anode, which needs surface preparation to increase lithium diffusion and impede the formation of dendrites. In this work, the formation of a thin LiZn layer on lithium metal using sputter deposition is reported. This method was selected due to the absence of solvents and by‐products generated during the modification, for its rapidity and because the formation of the alloy is performed in a clean and controlled atmosphere. Zinc has been chosen for its low cost and high Li+ ion diffusion coefficient of the corresponding LiZn alloy that is 1000 times higher than Li. Different parameters for the Zn deposition were investigated such as the distance between the Zn target and Li foil, the effect of substrate tilt and the direct current applied to the target. Electrochemical performance of LiFePO4/solid polymer electrolyte/Li ASSB demonstrated the superiority of the LiZn anodes and the clear influence of deposition parameters on the durability and performance at high C‐rates. Scanning electron microscopy images of the cross‐sectional view of LFP/SPE/Li stackings extracted from pouch cells after cycling showed an evident migration of Zn into the bulk Li metal anode as well as the formation of AlZn nanoparticles.