Effects of soluble polyimide (PI) binders on large-sized Li anodes (width = 21.5 cm; thickness = 40 μm) prepared using Li-metal powder (LiMP) have been investigated. PI binders form a uniform protective layer on exposed Li-powder-coated surfaces, thereby resulting in formation of scaffold-structured LiMP-based anodes. Uniform PI surface films favor realization of Li plating on Li-metal surfaces by forming a smooth surface structure, and the three-dimensional insulating PI matrix functions as a buffer layer that absorbs volume change. Moreover, PI binders facilitate enhanced cohesion between LiMP particles. The above-described triple action of PI binders significantly reduces Li dendrites. Consequently, PI-containing LiMP-based metal anodes demonstrate enhanced electrochemical performance compared to both polymeric binders and bare Li-metal foils. Results obtained in this study reveal that LiMP-based anodes containing PI binders exhibit 89% (98.2 mAh g–1) discharge-capacity retention during the 200th cycle, whereas bare Li-metal foil demonstrates sudden degeneration during the 65th cycle. Furthermore, PI containing LiMP-based anodes exhibit improved rate capability compared to other polymeric binders considered in this study.