We report an all-solid-state Li rechargeable battery based on a hybrid membrane comprising a highly-concentrated poly(ethylene carbonate) (PEC) electrolyte with 80 wt% of lithium bis(fluorosulfonyl)imide (LiFSI) and a three-dimensionally ordered macroporous polyimide matrix operating at room temperature. The PEC-LiFSI 80 wt% electrolyte showed an ionic conductivity of the order of 10 -5 S cm -1 at 30 o C and quite high Li transference number, and was employed as a good ion-conductive solid polymer membrane for all-solid-state Li battery. To assure the mechanical stability, the polyimide matrix was combined as a porous substrate to support the electrolyte. A Li|PEC-LiFSI|LiFePO 4 cell with the hybrid membrane delivered a reversible charge-discharge capacity close to 120~130 mAh g -1 at 30 o C and C/20 rate.