Abstract Electrochemical reduction of CO 2 to CH 3 OH is of great interest. Aerogels have fine inorganic superstructure with high porosity and are known to be exceptional materials. Now a Pd−Cu bimetallic aerogel electrocatalyst has been developed for conversion of CO 2 into CH 3 OH. The current density and Faradaic efficiency of CH 3 OH can be as high as 31.8 mA cm −2 and 80.0 % over the Pd 83 Cu 17 aerogel at a very low overpotential (0.24 V). The superior performance of the electrocatalyst results from efficient adsorption and stabilization of the CO 2 radical anion, high Pd 0 /Pd II and Cu I +Cu 0 /Cu II ratios, and sufficient Pd/Cu grain boundaries of aerogel nanochains.