Li metal batteries are promising next-generation energy storage systems due to their high theoretical energy density and low redox potential. However, their practical application is limited by Li dendrite formation during repeated cycling, which compromises safety and shortens cycle life. Herein, we introduce a flexible elastomeric Li metal anode that integrates a lithiophilic monolayer-assembled nano-crumpled surface with microscale concave architectures. This hierarchical design was realized by densely assembling metal nanoparticles onto thiol-functionalized elastomer, followed by Ni electroplating and subsequent assembly with lithiophilic amine-terminated molecular linkers. The resulting elastomeric anode effectively reduced Li nucleation overpotential and promotes mossy Li deposition. As a result, symmetric cells exhibited excellent cycling stability for over 2,100 h at 3 mA cm−2/3 mAh cm−2. Moreover, Li||LiFePO4 full cells retained ∼90.2% capacity after 1,000 cycles at 1C, demonstrating the potential of chemically and structurally engineered elastomeric anodes for durable and safe Li metal batteries.