Lithium-ion capacitors (LICs) which combine high energy density and high power density, are regarded as an energy storage device with great potential for development. Currently, the widely used electrolytes in LICs are liquid organic electrolytes. But they have serious safety issues and are less flexible. Herein, a highly porous gel electrolyte PVDF-HFP/PAN was prepared from polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and polyacrylonitrile (PAN), and their energy storage performance was investigated. The gel electrolyte-assembled pouch cell LICs offer superior cycling ability with a capacitance retention of 82% after 500 cycles and a high specific capacity of 40 mAh/g. In addition, the LICs based on PVDF-HFP/PAN gel electrolyte show good flexible properties. The overall merits of the gel electrolyte will provide a reference for the research of pouch cell LICs.