Assisted by the highly sensitive confocal microprobe Raman spectrometer and proper surface roughening procedure, the Raman investigation on the adsorption and reaction of methanol was performed on Pt-Ru electrodes with different coverages. A detailed description of the roughening process of the Pt electrodes and the underpotential deposition of the Ru was given. Reasonably good Raman signal reflecting the metal-carbon vibration and CO vibration was detected. The appearance of vibrations of the Ru oxides, together with the existence of Ru-C, Pt-C and CO bands, clearly demonstrates the participation of the bi-functional mechanism during the oxidation process of methanol on Pt-Ru electrodes. The Pt-Ru electrode was found to have a higher catalytic activity over Pt electrodes. This preliminary study shows that electrochemical Raman spectroscopy can be applied to the study of rough electrode surface.