AbstractA nanolayer of reactive propyl acrylate silane groups was deposited on a lithium surface by using a simple dipping method. The polymerization of cross‐linkable silane groups with a layer of ally‐ether‐ramified polyethylene oxide was induced by UV light. SEM analysis revealed a good dispersion of silane groups grafted on the lithium surface and a layer of polymer of about 4 μm was obtained after casting and reticulation. The electrochemical performance for the unmodified and modified lithium electrodes were compared in symmetrical Li/LLZO/Li cells. Stable plating/stripping and low interfacial resistance were obtained when the modified lithium was utilized, indicating that the combination of silane and polymer deposition is promising to increase Li‐metal/garnet contact.