Water-stable multi-layered lithium-doped carbon (Li x C6) negative electrode using poly(ethylene oxide) (PEO)-lithium bis(trifluoromethansulfonyl)imide (LiTFSI) polymer electrolyte containing N-methyl-N-propylpiperidinium bis(trifluoromethansulfonyl)imide (PP13TFSI) ionic liquid was developed. Electrochemical properties at 60 °C of the aqueous hybrid supercapacitor using activated carbon positive electrode and a multi-layered Li x C6 negative electrode (Li x C6 | PEO-LiTFSI | LTAP) without PP13TFSI exhibited performance similar to that using Li anode (Li | PEO-LiTFSI | LTAP). A drastic decrease in ESR was achieved by the addition of PP13TFSI to PEO-LiTFSI, allowing room temperature operation. The ESR of the multi-layered Li x C6 negative electrode with PEO-LiTFSI-PP13TFSI at 25 °C was 801 Ω cm2, which is 1/6 the value of the multi-layered Li negative electrode with PEO-LiTFSI (5014 Ω cm2). Charge/discharge test of the aqueous hybrid supercapacitor using multi-layered Li x C6 negative electrode with PEO-LiTFSI-PP13TFSI at 25 °C afforded specific capacity of 20.6 mAh (g-activated carbon)−1 with a working voltage of 2.7–3.7 V, and good long-term capability up to 3000 cycles. Furthermore, an aqueous hybrid supercapacitor consisting of a high capacitance RuO2 nanosheet positive electrode and multi-layered Li x C6 negative electrode with PEO-LiTFSI-PP13TFSI showed specific capacity of 196 mAh (g-RuO2)−1 and specific energy of 625 Wh (kg-RuO2)−1 in 2.0 M acetic acid-lithium acetate buffered solution at 25 °C.