The composite catalysts of Pd-MoO2/C for ethanol oxidation reaction (EOR) were prepared by microwave sintering. MoO3 was thermally reduced to MoO2 by carbon black in the preparing process of the Pd-MoO2/C material. The TEM analysis showed that Pd-MoO2 was well polymerized. Chronoamperometric, cyclic voltammetry, and electrochemical impedance spectra methods were applied to reveal the performance for EOR at room temperature. The Pd-MoO2/C electrode exhibited considerable high activity and stability. MoO2 as a co-catalyst significantly improved the catalytic activity of Pd-MoO2/C for EOR.