Polysaccharides are prospective hosts for the delivery and sequestration of bioactive guest molecules. Polysaccharides of dietary fiber, specifically cereal (1 → 3)(1 → 4)-β-glucans, play a role in lowering the blood plasma cholesterol level in humans. Direct host-guest interactions between β-glucans and conjugated bile salts are among the possible molecular mechanisms explaining the hypocholesterolemic effects of β-glucans. The present study shows that (1)H-(13)C NMR assays on a time scale of minutes detect minute signal changes in both bile salts and β-glucans, thus indicating dynamic interactions between bile salts and β-glucans. Experiments are consistent with stronger interactions at pH 5.3 than at pH 6.5 in this in vitro assay. The changes in bile salt and β-glucan signals suggest a stabilization of bile salt micelles and concomitant conformational changes in β-glucans.