Hierarchical hollow urchin-like nickel cobaltite (NiCo2O4) was synthesized using a two-step hydrothermal method. The effects of metal composition and surfactant addition on the morphology, structure, and electrochemical performance toward oxygen evolution reaction (OER) were investigated. The addition of cetyltrimethylammonium bromide (CTAB) reduced particle aggregation, resulting in a higher electrochemical active surface area and electrical conductivity. Lowering the Ni content from 1.0 to 0.25 did not alter the morphology and structure of the product to any extent. However, the crystallite size slightly increased. Among the spinels with different Ni and Co compositions, NiCo2O4 exhibited a superior OER electrocatalytic activity, achieving a 380 mV overpotential at 10 mA/cm2 current density. It also delivered a good performance in an anion exchange membrane water electrolyzer (AEMWE) using 1 M NaOH at 60 °C, reaching a current density of about 420 mA/cm2 at a cell voltage of 1.95 V.