Abstract Quasi-solid-state electrolytes encounter great obstacles in structural stability due to their inherent heterogeneity. Here, we introduce a new composite structure of glass-fiber-based metal-organic gel as a solid-state electrolyte and explore its electrochemical properties in lithium-metal batteries. We use a straightforward in-situ sol-gel method to synthesize this composite electrolyte, where glass fiber acts as matrices, ferric nitrate reacts with trimeric acid to form interconnected channels with abundant unsaturated metal sites, while ionic liquid electrolyte is in-situ confined into interconnected channels. The as-prepared composite electrolyte membrane has a uniform structure and composition, exhibiting a high room-temperature ionic conductivity of 1.79×10−3 S cm−1 and a high electrochemical oxidation potential of 4.76 V vs Li/Li+. This composite has excellent cycling performance in LiFePO4//Li (99.5% after 100 cycles) and NCM811//Li (86.6% after 200 cycles) batteries.