Engineering compositions, structures, and defects can endow nanomaterials with optimized catalytic properties. Here, we report that cobalt oxide (CoOx) ultrathin nanosheets (UTNS, ∼1.6 nm thick) with a large number of oxygen defects and mixed cobalt valences can be obtained through a facile one-step hydrothermal protocol. The large number of oxygen defects make the ultrathin CoOx nanosheet a superior OER catalyst with low overpotentials of 315 and 365 mV at current densities of 50 and 200 mA cm-2, respectively. The stable framework-like architectures of the UTNS further ensure their high OER activity and durability. Our method represents a facile one-step preparation of CoOx nanostructures with tunable compositions, morphologies, and defects, and thus promotes OER properties. This strategy may find its wider applicability in designing active, robust, and easy-to-obtain catalysts for OER and other electrocatalytic systems.