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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.