Superior quality, clean-tasting food grade polydextrose is prepared by reacting glucose or glucose-containing materials such as hydrolyzed starch with a polyol such as sorbitol in the presence of low levels of a polycarboxylic acid such as citric acid. In one embodiment, polydextrose is prepared by reacting glucose or glucose-containing materials such as hydrolyzed starch with a polyol such as sorbitol in the presence of low levels, i.e., from about 0.03% to about 0.1% citric acid at a temperature of from about 145 to about 185 C., preferably from about 150 C. to about 160 C. Because of the low levels of catalyst used in preferred embodiments, minimal or no off-flavors and little color are formed during the course of the reaction, but the product may be purified using ion exchange, membrane filtration, or carbon treatment, or further modified by hydrogenation if desired for certain applications.