Polymer-electrolyte fuel cell supplying CO2 was demonstrated. Using a PEFC, 95 mol% of methanol was selectively formed by supplying H-2 to Pt catalyst and CO2 to Zn-Cu-Ga layered double hydroxide catalyst accompanying protons and electrons transfer, i.e. H-2 -> 2H(+) + 2e(-) at anode followed by CO2 + 6H(+) + 6e(-) -> CH3OH + H2O at cathode. Using PEFC, CO2 reduction with water was also enabled to methanol (100-86 mol%) in contrast that negligible amount of methanol was formed if mixed oxidation and reduction catalysts were under CO2 and moisture. At anode, water was dissociated over Pt catalyst to provide protons (H2O -> OH(adsorbed) + H+ e(-)) that transferred to Zn-Cu-Ga catalysts at cathode on which CO2 was progressively reduced to methanol (CO2 + 6H(+) + 6e(-) -> CH3OH + H2O). (c) 2012 Elsevier B.V. All rights reserved.