The design and development of efficient and robust water oxidation catalysts based on earth-abundant elements are crucial for energy conversion and storage technology. Herein, we report Co3O4 porous nanocages derived from simple metal-organic frameworks by a simple self-assemble method and a low temperature anneal process. This method can synthesize MxCo3−xO4 (M = Co, Mn, Fe) porous nanocages materials and allow precise control of ratio of substituted metal in Co3O4 catalysts. These catalysts were investigated for photochemical, chemical-driven (cerium (IV)-driven) and electrochemical water oxidation, and they presented a superior activity for water oxidation. The high turnover frequency (TOF) of ∼3.2 × 10 -4 s -1 per Co atom was obtained under neutral pH using Co3O4 porous nanocages in photocatalytic water oxidation reaction, which is comparable with those of nanostructured Co3O4 clusters supported on mesoporous silica. Under cerium (IV)-driven water oxidation condition, a high TOF of ∼3.6 × 10 −3 s −1 per Co atom was achieved, which was the highest among those of other known reported cobalt oxides. The overpotential of Co3O4 porous nanocages for the electrochemical water oxidation (η = 0.42 V at 1 mA cm -2 ) is comparable to the reported overpotentials of catalysts based on cobalt. Multiple experimental results (e.g. XRD, TEM, HR-TEM and XPS) confirm that Co3O4 porous nanocages are highly stable. This study illustrates a guideline to the design and synthesis of inexpensive and highly active spinel catalysts for water oxidation. 6,40-46 Figure 1. Schematic representation of (a) polyhedral representation of Co 3 O 4 (b) ball-and-stick representation of Co 3 O 4 (c) ball-and-stick representation of Co 4 O 4 core in spinel Co 3 O 4 (d) Mn 4 CaO 5 in the photosystemⅡ-WOC. Turquoise: Co 3+ ; teal: Co 2+ ; red: O; violet: Mn; brown: Ca.