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The integration of organic and inorganic building blocks into hierarchical porous architectures makes potentially desirable electrocatalytic materials in many electrochemical applications due to their combination of attractive qualities of dissimilar components and well-constructed charge transfer pathways. Herein, we demonstrate the preparation of the hierarchical porous Co₃O₄@graphene (Co₃O₄@G) microspheres by one-step hydrothermal method to achieve high electrocatalytic performance for enzyme-free biosensor applications. The obtained Co₃O₄@G microspheres are consisted of the interconnected networks of Co₃O₄ and graphene sheets, and thus provide large accessible active sites through porous structure, while graphene sheets offer continuous electron pathways for efficient electrocatalytic reaction of Co₃O₄. These structural merits with synergy effect of Co₃O₄ and graphene lead to a high …