It is of great significance to reveal the influence of small differences in the coordination environments of metal ions in the catalytic active centers on the selectivity of products in the electrocatalytic CO 2 reduction reaction (CO 2 RR). Here, two types of metal−organic frameworks (MOFs) based on square-pyramidal CuO 5 and square-planar CuO 4 nodes, respectively, are compared in regard to their performances in electrocatalytic CO 2 RR. The MOF (Cu-DBC, H 8 DBC = dibenzo-[g,p]chrysene-2,3,6,7,10,11,14,15-octaol) constructed by CuO 5 nodes and the catechol-derived ligands exhibit high performance for the electrocatalytic reduction of CO 2 to CH 4 with a Faradaic efficiency of 56% and a current density of 11.4 mA cm −2 at −1.4 V vs RHE. In comparison, two other MOFs, Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) and Cu-THQ (THQ = tetrahydroxy-1,4-quinone), constructed by CuO 4 and catechol-derived ligands, exhibit that CO is the sole reduced product. Theoretical calculations and Cu L-edge adsorption spectroscopy revealed that the energy levels of metal d-orbitals (d z 2 , d xz , and d yz ) in the square-pyramidal CuO 5 site are elevated compared to those in the squareplanar CuO 4 site. As a result, the CuO 5 active sites can strongly adsorb *CO intermediates and hence facilitate the hydrogenation of *CO into *CHO, which is beneficial for yielding CH 4 instead of CO. This work will be helpful to understand the mechanism of copper-based catalysts for the electrocatalytic reduction of CO 2 to hydrocarbons.