Among the products of the electrocatalytic reduction of carbon dioxide (CO2RR), CO is currently the most valuable product for industrial applications. However, poor stability is a significant obstacle to CO2RR. Therefore, we synthesized a series of bimetallic organic framework materials containing different ratios of tungsten to copper using a hydrothermal method and used them as precursors. The precursors were then subjected to pyrolysis at 800 °C under argon gas, and the M-N bimetallic sites were formed after 2 h. Loose porous structures favorable for electrocatalytic reactions were finally obtained. The material could operate at lower reduction potentials than existing catalysts and obtained higher Faraday efficiencies than comparable catalysts. Of these, the current density of WCu-C/N (W:Cu = 3:1) could be stabilized at 7.9 mA ‧ cm-2 and the FE of CO reached 94 % at a hydrogen electrode potential of -0.6 V (V vs. RHE). The novel materials made with a two-step process helped to improve the stability and selectivity of the electrocatalytic reduction of CO2 to CO, which will help to promote the commercial application of this technology.