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) micro spheres 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 performance of enzyme-free detection for glucose: high sensitivity, good selectivity, and remarkable stability. (C) 2016 Elsevier B.V. All rights reserved.