Methanol electrochemical oxidation in a direct methanol fuel cell (DMFC) is considered to be an efficient pathway for generating renewable energy with low pollutant emissions. NiO−CuO and Ni0.95Cr0.05O2+δ thin films were synthesized using a simple dip-coating method and tested for the electro-oxidation of methanol. These synthesized electrocatalysts were characterized by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS), and Raman spectroscopy. Different electrochemical techniques were used to investigate the catalytic activity of these prepared electrocatalysts for methanol oxidation, including linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and chronoamperometry (CA). In the presence of 0.3 M methanol, the current densities of NiO−CuO and Ni0.95Cr0.05O2+δ thin films were found to be 12.2 mA·cm−2 and 6.5 mA·cm−2, respectively. The enhanced catalytic activity of NiO−CuO and Ni0.95Cr0.05O2+δ thin films may be a result of the synergistic effect between different metal oxides. The Chronoamperometry (CA) results of the mixed metal oxide thin films confirmed their stability in basic media. Furthermore, the findings of electrochemical impedance spectroscopy (EIS) of mixed metal oxide thin films demonstrated a lower charge transfer resistance as compared to the pure NiO, CuO, and Cr2O3 thin films.