A gradual downshift and asymmetric broadening of the Si optical phonon peak were observed by Raman scattering measurements of continuously thermally oxidized silicon nanowires (SiNWs) synthesized by laser ablation. This downshift and broadening can be interpreted by the phonon confinement effect. Further thermal oxidation produced a reverse change; namely, an upshift of the optical phonon peak. This is considered to be due to compressive stress since this stress was relieved by removing the oxide layers formed around the SiNW cores, resulting in a downshift of the optical phonon peak.