This method measures the polydextrose content of foods. Polydextrose is a 1 kcal/g randomly bonded polysaccharide used as a food ingredient, and has physiological benefits consistent with dietary fiber. The value obtained from this polydextrose assay may be added to the values from the enzyme-gravimetric methods without concern for double counting. Polydextrose is extracted from food with hot water and centrifuged. The supernatant then passes through a centrifugal ultrafilter to remove high molecular weight interferences. The filtrate is treated with an enzyme mix (isoamylase, amyloglucosidase, and fructanase) to remove any oligosaccharide interferences, mainly maltooligomers and fructans. Polydextrose standards undergo the same treatment. High-pressure anion-exchange chromatography with electrochemical detection (HPAEC-ED) is used to detect and quantitate the high molecular weight fraction of polydextrose.