The emphasis in the present study was placed on developing Raman spectroscopy into a versatile technique, whichoffers intriguing opportunities for investigating electrocatalytic reaction. Through the in-situ Raman spectroscopicstudy, with a confocal Raman microscope, on the methanol electrooxidation on platinum electrodes with varioussurface roughness, it has shown the advantage in obtaining the informative spectra during the surface reaction withhigh faradaic current. This is hard to be performed by the other spectroscopic methods that have to use the thin-layercell. The ability to obtain both the low frequency and the high frequency vibrations of Pt-C and C O bands allowsthe assignment of surface species unambiguously. The ease of studying the surface bonding, investigating highlyroughened surfaces with dark color and using high concentration electrolyte may provide a way to bridge the gapbetween the systems of fundamental research and practical applications. The results reveal the surface roughnesseffect on the electrooxidation process and provide clear evidence for the parallel oxidation mechanism.