CuCo2O4 films with different morphologies of either mesoporous nanosheets, cubic, compact‐granular, or agglomerated embossing structures are fabricated via a hydrothermal growth technique using various solvents, and their bifunctional activities, electrochemical energy storage and oxygen evolution reaction (OER) for water splitting catalysis in strong alkaline KOH media, are investigated. It is observed that the solvents play an important role in setting the surface morphology and size of the crystallites by controlling nucleation and growth rate. An optimized mesoporous CuCo2O4 nanosheet electrode shows a high specific capacitance of 1658 F g−1 at 1 A g−1 with excellent restoring capability of ≈99% at 2 A g−1 and superior energy density of 132.64 Wh kg−1 at a power density of 0.72 kW kg−1. The CuCo2O4 electrode also exhibits excellent endurance performance with capacity retention of 90% and coulombic efficiency of ≈99% after 5000 charge/discharge cycles. The best OER activity is obtained from the CuCo2O4 nanosheet sample with the lowest overpotential of ≈290 mV at 20 mA cm−2 and a Tafel slope of 117 mV dec−1. The superior bifunctional electrochemical activity of the mesoporous CuCo2O4 nanosheet is a result of electrochemically favorable 2D morphology, which leads to the formation of a very large electrochemically active surface area. The direct growth of shape‐controlled CuCo2O4 electrodes on a 3D architecture of Ni foam is achieved via a hydrothermal growth technique using various solvents, followed by air annealing treatment. The high bifunctional electrochemical activity of the mesoporous CuCo2O4 nanosheet is a result of the electrochemically favorable 2D morphology, which leads to the formation of a very large electrochemically active surface area.