A facile and low cost molten salt method for the synthesis of Co@Co(OH)2 core-shell nanostructured material exhibiting high specific capacitances for supercapacitors was developed. In our conditions, the molten salt acted as solvent and reducing agent for the precipitation and formation of Co-based nano-structures. It was observed that in the Co@Co(OH)2 core-shell nanostructure, Co cores can act as a conductive medium to improve the utilization of Co(OH)2 due to the superior electrical conductivity of Co metal and its high surface area. It was also found that the as-prepared Co@Co(OH)2 exhibited high electrochemical performance as a cathode material in asymmetric supercapacitors, yielding specific capacitance values of up to ~410 F g−1 at 2 A g−1 with a retention rate of 90 % after 2500 cycles. The achievement of high capacitance coupled to a low cost method represents an important step forward in the development of promising electrode materials for alkaline supercapacitor cathodes.