Metal organic frameworks (MOFs) are considered as promising electrocatalytic materials because of its good designability and structural diversity. Herein, the composite materials of Cu2S/Ni3S2@Ni-BDC/NF are successfully synthesized through the hydrothermal and electrodeposition methods. The distinctive heterostructure provides ample active sites and retains structural integrity to promote durability. When it is explored as bifunctional electrocatalyst, the overpotential of 63 mV at 10 mA cm−2 current density for the hydrogen evolution reaction (HER), the overpotential of 353 mV at 50 mA cm−2 current density for the oxygen evolution reaction (OER). In a two-electrode system, an extremely low cell voltage of 1.55 V is required to achieve 20 mA cm−2 current density. Moreover, Cu2S/Ni3S2@Ni-BDC exhibits satisfactory glucose sensitivity of 56,220 μA mM−1 cm−2 and outstanding anti-interference performance. This design not only successfully constructs 0D/2D heterogeneous interface of electrocatalyst, but also demonstrates the multifunctional application potential of water splitting and glucose electrochemical sensors.