Lithium metal batteries (LMBs) with solid polymer electrolytes (SPEs) offer higher energy density and enhance safety compared to the Li-ion batteries that use a graphite anode and organic electrolytes. However, achieving long cycle life for LMBs while enabling the use of high-voltage cathodes required the compatibility between cathode-SPE, rather than focusing solely on the individual components. This study presente a dual-functional poly(ionic liquid) (PolyIL)-based material that simultaneously serves as an SPE matrix and a cathode binder, constructing a cathode-SPE interface with exceptional (electro)chemical compatibility owing to the high ionic conductivity and wide electrochemical stability window. Additionally, a modified cellulose acetate (CA)-based PolyIL substrate, enriched with C═O and ─OH groups, is designed rationally and incorporated to assist the Li+ migration, leveraging their highly negative charge, and enhancing the mechanical strength of the SPE. Furthermore, an in situ polymerization approach is employed to assemble the cells, improving the physical compatibility at the cathode-SPE interface. As a result, the Li||LFP cell demonstrate stable cycling beyond 1100 cycles, and the Li||NCM811 cell reliably operates at a high cut-off voltage of up to 4.8 V.