Abstract: An optical waveguide comprises an anhydrous synthetic silica glass substrate 1, which contains less than a predetermined concentration of hydroxyl group, a core waveguide 2 having a rectangular cross-section being formed on the substrate 1, and a cladding layer 3 having a lower refractive index thereof than the core waveguide 2 being covered by the cladding layer 3. The concentration of hydroxyl group contained in a synthetic silica glass substrate of an optical waveguide or an optical device is essentially less than 300 ppm, preferably less than 100 ppm, more preferably less than 50 ppm.