Structural parameters of pectin (a polysaccharide and important component of dietary fibre) influence the interaction with bile acids (BA). The effect of experimental conditions (concentration of pectin, BA and Ca2+) on such interactions was studied at pH 6.0. Series of pectins were used, prepared from virtually fully esterified pectin by gradual de-esterification with alkali or with pectinesterase from oranges. Further amidated and acetylated pectins were also tested. The greatest interaction with BA was found with a very highly esterified pectin under in vitro conditions. The interaction diminished with decreasing degrees of esterification (DE). This decrease was more intensive for pectins possessing a blockwise arrangement of free -COOH groups. Derivatives of pectin generally interacted less with BA. These results were principally confirmed with commercial pectins, with pectins prepared on a pilot-plant scale and with pectins originating from a defined botanical source. The interactions of these preparations with BA were less intensive than with those of pectins having an ideal random distribution of free -COOH groups in the polysaccharide molecules at the same DE. The interaction with pectin is also likely to be influenced by the structure of BA.