Copper and nickel hexacyanoferrate (CuHCF and NiHCF) nanostructures featuring three-dimensional open-framework tunnels are prepared using a solution-based coprecipitation process. CuHCF shows superior supercapacitive behavior than the NiHCF, due to the presence of numerous macropores in CuHCF particles for facilitating the transport of electrolyte. Both CuHCF and NiHCF electrodes with stainless steel (SS) substrate tend to lose their electroactivity towards intercalation/deintercalation of hydrated potassium ions owing to the partial corrosion of SS. Formation of a protective and conductive carbon layer in between SS and CuHCF (NiHCF) film is of paramount importance for improving the irreversible loss of electroactivity. Thin and compact graphene (GN) layer without observable holes in its normal plane is the most effective way to suppress the corrosion of SS compared with porous carbon nanotube and activated carbon layers. Specific capacitance of CuHCF electrode with GN layer (CuHCF/GN/SS) reaches 570 F g(-1), which is even better than that of CuHCF with Pt substrate (500 F g(-1)) at 1 A g(-1). The CuHCF/GN/SS exhibits high stability with 96% capacitance retention over 1000 cycles, greater than the CuHCF with Pt (75%). (C) 2015 Elsevier B.V. All rights reserved.