The hierarchical CuCo2O4/C microspheres have been fabricated via a two-step method involving hydrothermal and calcination processes. SEM, TEM, HRTEM, XRD and XPS were used to characterize the morphology, structure, and composition of the materials. The CuCo2O4/C microspheres have a hierarchically flower-like structure composed of nanoparticles-stacked nanosheets. Moreover, the as-prepared double-metal oxide hierarchical microsphere composites exhibit greatly improved electrochemical performance than that of pure CuCo2O4, owing to the synergistic effect of CuCo2O4 and carbon spheres. The CuCo2O4/C 5:1 modified electrode exhibited high sensitivity of 707.71 mu A mM(-1)cm(-2) in a wide linear range from 5 to 8000 mu M with detection limit of about 1.5 mu M. The outstanding glucose sensing performance of CuCo2O4/C 5:1 demonstrated that this kind of spinel bimetallic oxides composites can be favorable candidates for the development of non-enzymatic sensor.