AbstractIt is shown that diethylaminoethyl‐cellulose (DEAE‐cellulose) columns can be used for efficient chromatographic fractionation of polysaccharide mixtures. At about pH 6 neutral polysaccharides are not or only weakly adsorbed by DEAE‐cellulose. They can be readily eluted at the same pH by buffers of increasing strength. Neutral polysaccharides are adsorbed by DEAE‐cellulose in the hydroxyl form and can be fractionated by elution with NaOH of increasing strength. Acidic polysaccharides like pectic acid are adsorbed readily at neutral and weakly acidic pH values, but can only be eluted by increasing the pH. The use of the borate form of DEAE‐cellulose and elution with Na‐borate of increasing strength increases the fractionation effect. Examples are given for the fractionation of wheat starch dextrin, a mixture of sugar beet araban and pectic acid, sugar beet pectic acid, a mixture of wheat pentosan and serum albumin, and of the cold water‐soluble wheat flour po