Intensive research in the area of electrochemical energy storage (EES) in the past decade has been inspired by the demand for EES in handheld electronic devices, transportation, and storage of renewable energy for the power grid. It has become necessary to find novel electrode materials with high performance, low cost and advanced electrode architecture to meet the large-scale commercial applications of EES. We developed a facile, green and energy-saving technique to fabricate cost-effective nanostructured NiCo₂O₄ supported on Ni foam (NiCo₂O₄/Ni foam) with a unique microstructure. As a binder-free electrode material, a high specific capacitance of 760 F g⁻¹ was achieved with excellent cyclability at a current density of 1 A g⁻¹. In conjunction with the superior electrode architecture, the nanoplate-like NiCo₂O₄/Ni foam with optimal performance has the potential to meet the needs of its wide commercial application for high-efficiency EES. The preparation method may be extended to other metal oxide/hydroxide-based materials with outstanding nanostructures for electronic, magnetic, optical, photochemical, and catalytic applications.