In this work, we have adopted a facile three-step method for constructing an intriguing bifunctional electrode of self-supported hollow (Ni,Co)Se2 arrays with a metal-organic framework (MOF) precursor. The triangle-like cobalt-based MOF arrays are first grown on a carbon cloth at room temperature, which is followed by an ion exchange/etching process with Ni(NO3)2 to form a critical hollow nanostructure with an incorporated hetero-metal element. The intermediate is then transformed into the final product through solvothermal selenization treatment. Taking advantages of the structural and compositional merits as well as the self-supporting nature, the resultant (Ni,Co)Se2 electrode exhibits excellent electrochemical activity and stability. When tested as an electrocatalyst for the oxygen evolution reaction (OER), the (Ni,Co)Se2 array electrode displayed a low onset overpotential of 226 mV and a small overpotential of 256 mV to afford a current density of 10 mA cm-2. The (Ni,Co)Se2 electrode is also utilized in a supercapacitor, which delivers a high specific capacitance of 2.85 F cm-2 at 2 mA cm-2 and exhibits excellent cycling stability with a capacitance retention of 80.8% after 2000 charge-discharge cycles at 20 mA cm-2. These results demonstrate the significance of the rational design of electrode materials and disclose the potential of our MOF-derived hollow (Ni,Co)Se2 array electrode for a variety of practical applications in energy conversion and storage.