Abstract Bifunctional electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline electrolyte may improve the efficiency of overall water splitting. Nickel cobaltite (NiCo 2 O 4 ) has been considered a promising electrode material for the OER. However, NiCo 2 O 4 that can be used as an electrocatalyst in HER has not been studied yet. Herein, we report self‐assembled hierarchical NiCo 2 O 4 hollow microcuboids for overall water splitting including both the HER and OER reactions. The NiCo 2 O 4 electrode shows excellent activity toward overall water splitting, with 10 mA cm −2 water‐splitting current reached by applying just 1.65 V and 20 mA cm −2 by applying just 1.74 V across the two electrodes. The synthesis of NiCo 2 O 4 microflowers confirms the importance of structural features for high‐performance overall water splitting.