A flexible and self-healing supercapacitor with high energy density in low temperature operation was fabricated using a combination of biochar-based composite electrodes and a polyampholyte hydrogel electrolyte. Polyampholytes, a novel class of tough hydrogel, provide self-healing ability and mechanical flexibility, as well as low temperature operation for the aqueous electrolyte. Biochar is a carbon material produced from the low-temperature pyrolysis of biological wastes; the incorporation of reduced graphene oxide conferred mechanical integrity and electrical conductivity and hence the electrodes are called biochar-reduced-graphene-oxide (BC-RGO) electrodes. The fabricated supercapacitor showed high energy density of 30 Wh/kg with ~90% capacitance retention after 5000 charge-discharge cycles at room temperature at a power density of 50 W/kg. At -30 °C, the supercapacitor exhibited an energy density of 10.5 Wh/kg at a power density of 500 W/kg. The mechanism of the low-temperature performance excellence is likely to be associated with the concept of non-freezable water near the hydrophilic polymer chains, which can motivate future researches on the phase behaviour of water near polyampholyte chains. We conclude that the combination of the BC-RGO electrode and the polyampholyte hydrogel electrolyte is promising for supercapacitors for flexible electronics and for low temperature environments.