Hydrogen peroxide electroreduction on both catalytically active Pt and inactive Au surfaces are studied by using both surface-enhanced Raman spectroscopy (SERS) and density functional theory (DFT) calculations. SERS measurements on Pt show the presence of Pt-OH at negative potentials, which suggests that hydroxide is formed as an intermediate during the electroreduction process. Additionally, the O-O stretch mode of H2O2 is observed on Pt, which shifts to lower energy as potential is swept negatively, indicating that the O-O bond is elongated. For comparison, there is no variation in the energy of the same O-O mode on Au surfaces, and there is no observation of Au-OH. DFT calculations show that H2O2 adsorption on Pt(110) results in the dissociation of O-O bond and the formation of Pt-OH bond. On Au, O-O bond elongation is calculated to occur only on the (110) face. However, the magnitude of the elongation is much smaller than that found on Pt(110).