Partial oxidation of methanol was performed with a gas-phase [CH3OH|H3PO4|O-2] cell reactor by using noble metals as electrocatalysts over the temperature range of 343-373 K. Among the noble metal electrocatalysts tested, the Ir (anode)-Pt (cathode) combination showed the best cell performance for partial oxidation of methanol into dimethoxymethane (DMM) and methyl formate (W). The cell gave a maximum current density of 34 mA cm(-2) at 373 K; one-pass conversion of methanol was 14% and the turn-over number per Ir was 6.6 h(-1). The kinetic results of the oxidation of methanol with the [CH3OH, Ir|H3PO4|Pt, O-2] cell could be explained in terms of the reaction mechanism proposed. In general, the cell performance in the oxidation of methanol for different combinations of anode-cathode electrocatalysts was strongly deteriorated with the diffusion of methanol from the anode to the cathode (cross-over). However, the cell of Ir (anode)-Pt (cathode) combination was specifically resistant to this unfavorable effect. (C) 2003 Elsevier Science B.V. All rights reserved.