In this work, Ni(OH)2 nanoplates grown on the Cu substrate were synthesized and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Then a novel Cu–Ni(OH)2 modified glass carbon electrode (Cu–Ni(OH)2/GCE) was fabricated and evaluated by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and typical amperometric response (i–t) method. Exhilaratingly, the Cu–Ni(OH)2/GCE shows significant electrocatalytic activity toward the reduction of H2O2. At an applied potential of −0.1V, the sensor produces an ultrahigh sensitivity of 408.1μAmM−1 with a low detection limit of 1.5μM (S/N=3). The response time of the proposed electrode was less than 5s. What's more, the proposed sensor displays excellent selectivity, good stability, and satisfying repeatability.