In-situ electrochemical surface-enhanced Raman scattering (EC-SERS) measurement is a powerful tool to investigate characteristic chemical reactions via multi-electron transfer, especially effective under localized plasmon excitation. Au and Ag nanostructured semiconductors show photoelectric effect under the illumination of visible and near-infrared light. It has been suggested that the effect is due to the exciton generations of the metal nanostructure on n- and p-type semiconductors induced by localized surface plasmons resonances. Plasmon active nanostructured semiconductor electrodes enable water oxidation or reduction via multiple holes or electrons transfer. In this work, EC-SERS from the intermediate species at water oxidation and reduction process at the electrode-electrolyte interface under near-infrared light illumination.