A new type of amorphous barium aluminum oxide was synthesized using a polyol thermal method involving a mixture with Vulcan XC-72 carbon and supported with 20%Pt catalysts to enhance the activity of a methanol electrooxidation reaction (MOR). The maximum current density, electrochemically active surface area (ECSA), and electrochemical impedance spectra (EIS) of the obtained catalysts for MOR were determined. The MORs of barium aluminum oxide with different calcination temperatures and Ba and Al contact ratios were studied. The MOR of the uncalcined amorphous Ba0.5AlOx catalysts prepared with a mole ratio of 2/1 Ba/Al mixed with Vulcan XC-72 carbon and supported with 20%Pt catalyst (Pt-Ba0.5AlOx/C) was enhanced compared with that of 20%Pt-Al2O3/C and 20%Pt/C catalysts due to its obtained largest maximum current density of 3.89 mA/cm2 and the largest ECSA of 49.83 m2/g. Therefore, Pt-Ba0.5AlOx/C could provide a new pathway to achieve a sufficient electrical conductivity, and possible synergistic effects with other active components improved the catalytic activity and stability of the prepared catalyst in MOR.