The Ag/Ni(OH)2 composite electrode has been designed and in situ constructed on a copper substrate by combining electroless deposition technology with electrodeposition. The products can be directly used as a high performance binder free electrode. The synergistic effect between the Ag nanocubes (AgNCs) as backbones and the deposited Ni(OH)2 as the shell can significantly improve the electrochemical properties of the composite electrode. Moreover, this in situ growth strategy forms a strong bonding force of active materials to the substrate, which can improve the cycling performance and lower the equivalent series resistance. The Ag/Ni(OH)2 composite electrode exhibits enhanced electrochemical properties with a high specific capacitance of 3.704 F cm−2, coulombic efficiency of 88.3% and long-term cyclic stability.