Electrochemical water splitting using hollow and defect-rich catalysts has emerged as a promising strategy for efficient hydrogen production. However, the rational design and controllable synthesis of such catalysts with intricate morphology and composition present significant challenges. Herein, we propose a template-engaged approach to fabricate a novel ball-in-ball hollow structure of Co-P-O@N-doped carbon with abundant oxygen vacancies. The synthesis process involves the preparation of uniform cobalt-glycerate (Co-gly) polymer microspheres as precursors, followed by surface coating with ZIF-67 layer, adjustable chemical etching by phytic acid, and controllable pyrolysis at high temperature. The resulting ball-in-ball structure offers a large number of accessible active sites and high redox reaction centers, facilitating efficient charge transport, mass transfer, and gas evolution, which are beneficial for the acceleration of electrocatalytic reaction. Additionally, density functional theory (DFT) calculations indicate that the incorporation of oxygen and the presence of Co-P dangling bonds in CoP significantly enhance the adsorption of oxygenated species, leading to improved intrinsic electroactivity at the single-site level. As a sequence, the titled catalyst exhibits remarkable electrocatalytic activity and stability for water splitting in alkaline media. Notably, it only requires a low overpotential of 283 mV to achieve a current density of 10 mA cm-2 for the oxygen evolution reaction. This work may provide some new insights into the design of complex hollow structures of phosphides with abundant defects for energy conversion.