Alternative green binders processable in water are being investigated for the development of more efficient and sustainable supercapacitors. However, their electrochemical performances have fallen within or below the average of commercially available devices. Herein, an optimised gelled mixture of graphene oxide (GO) and starch, a biopolymer belonging to the family of polysaccharides, is proposed. The molecular interactions between the two components enhance electrodes structure and morphology, as well as their thermal stability. GO, thanks to its reduction that is initially triggered by reactions with starch and further progressed by thermal treatment, actively contributes to the charge storage process of the supercapacitors. The optimised electrodes can deliver a specific capacitance up to 173.8 F g−1 while providing good rate capabilities and long-term stability over 17,000 cycles. These are among the best electrochemical performances achieved by environmentally friendly supercapacitors using a biomaterial as a binder.