The sorption of moisture by different cellulose derivatives was examined as a function of relative humidity, to evaluate the influence of counter-ions and different charged groups on the moisture adsorption mechanism. Studies were made on cellulosic materials containing sulfate (-O-SO3H) and carboxylic (-COOH) groups in different ionic forms (H+, Li+, Na+, K+ and Ca2+). Uncharged cellulose and amylose were also examined for comparison. It was shown that the choice of counter-ions had a large influence on the moisture uptake by the studied polymers. Moisture adsorption by cellulose containing sulfate acid groups was favoured by the counter-ion H+, rather than, in order of decreasing efficiency, by Li+, Na+, Ca2+ and K+. Two types of differently adsorbed water were found : non-freezing bound water and freezing bound water. Most of the differences in total moisture content were due to differences in the freezing water content. The counter-ion favouring water adsorption in the case of the cellulose containing carboxylic acid groups was Li+, followed, in decreasing order of efficiency, by Na+, K+, Ca2+ and H+. In this case, the differences in total water content were found in both the non-freezing and freezing water. It was furthermore shown that the presence of charged groups was necessary for the adsorption of freezing water when the relative humidity was less than 100%. The large influence of the counter-ions on water adsorption may be associated with the ionic radius (size of the counter-ion), which influences the degree of hydration. Differences in water adsorption for the protonated form may be explained by the observation that carboxylic acids are weak acids with limited dissociation, whereas the stronger sulfate acid groups facilitate a more complete dissociation.