Supercapacitors and batteries are essential for sustainable energy development. However, the bottleneck is the associated high cost, which limits bulk use of batteries and supercapacitors. In this context, realizing that the cost of energy storage device mainly depends on materials, synthesis processes/procedures, and device fabrication, an effort is made to rationally design and develop novel low-cost electrode materials with enhanced electrochemical performance in asymmetric supercapacitors. Herein, surface functionalization approach is adopted to design low-cost 3D mesoporous and nanostructured nickel–nickel oxide electrode materials using facile synthesis for application in supercapacitors. It is demonstrated that the 3D mesoporous Ni provides the high surface area and enhanced ionic conductivity, while germanium functionalization improves the electrical conductivity and reduces the charge-transfer resistance of NiO. Surface functionalization with Ge demonstrates the significant improvement in specific capacitance of NiO. The asymmetric supercapacitor using these Ge functionalized NiO–Ni electrodes provides a specific capacitance of 304 Fg 1 (94 mFcm 2), energy density of 23.8Whkg 1 (7.35μWhcm 2), and power density of 6.8 kW kg 1 (2.1mWcm 2) with excellent cyclic stability of 92% after 10000 cycles. To validate their practical applications, powering the digital watch using the asymmetric supercapacitors in laboratory conditions is demonstrated.