Non-enzymatic glucose detection is an effective strategy to control the blood glucose level of diabetic patients. A novel hierarchical core-shell structure of nickel hydroxide shell coated copper hydroxide core based on copper foam (Ni(OH)@Cu(OH)-CF) was fabricated and derived from NiO@CuO-CF for glucose sensing. Cyclic voltammetry and amperometry experiments have demonstrated the efficient electrochemical catalysis of glucose under alkaline conditions. The measurement displays that the fabricated sensor exhibits a detection scale of 0.005-4.5 mM with a detection sensitivity of 4.67 µA/µM/cm. It has remarkable response/recovery times in respect of 750 μM glucose (1.0 s/3.5 s). Moreover, the NiO@CuO-CF shows significant selectivity, reliable reproducibility and long-term stability for glucose determination, suggesting it is a suitable candidate for further applications.