Abstract A procedure is described whereby the proportion of hexose: pentose in solution may be determined spectrophotometrically. The method uses the phenol‐sulphuric acid reaction and a previously unreported ultraviolet adsorption band at 312‐325 nm in the reacted solutions. The λmax of this band increases with, and is linearly related to, the ratio of hexose to total sugars in the mixture, in the range 10‐80% hexose.