Bilirubin, a bile pigment, was studied for its extent of adsorption on substituted aminechloromethyl polystyrene by UV spectrophotometry. By performing simple displacement reactions on chloromethyl polystyrene with secondary and tertiary amines, the amount of charge density and steric factor on substituted nitrogen atom have been varied. Adsorption isotherms of bilirubin at 0°C by different amine–chloromethyl polystyrene homologs suggest the existence of electrostatic interaction of polymeric resin with bilirubin moiety. Results of adsorption of bilirubin to polymeric resin have shown that the extent of adsorption of bilirubin depends on the unit charge, and on the structure of the substituted amine–chloromethyl polystyrene. The effects of porosity of resin on bilirubin adsorption have also been discussed.