The construction of an efficient catalyst for electrocatalytic reduction of CO₂ to high value-added fuels has received extensive attention. Herein, nitrogen-doped mesoporous carbon (NMC) was used to support CuSb to prepare a series of materials for electrocatalytic reduction of CO₂ to CH₄. The catalytic activity of the composites was significantly improved compared with that of Cu/NMC. In addition, the Cu content also influenced the activity of electrocatalytic CO₂ reduction reaction. Among the materials used, the CuSb/NMC-2 (Cu: 5.9 wt%, Sb: 0.49 wt%) catalyst exhibited the best performance for electrocatalytic CO₂ reduction, and the faradaic efficiency of CH₄ reached 35%, and the total faradaic efficiency of C1–C2 products reached 67%.