The oxidation state of chromium in glasses melted in an air atmosphere with and without refining agents was investigated by Cr K-edge X-ray absorption near-edge structure (XANES) and optical absorption spectroscopy. A good agreement in the relative proportion of Cr(III) and Cr(VI) is obtained between both methods. We show that the chemical dependence of the absorption coefficient of Cr(III) is less important in XANES than in optical absorption spectroscopy. The comparison of optical absorption and XANES spectra of glasses melted under different conditions provides an indirect assessment of the molar extinction coefficient of Cr(VI) in glasses.