Résumé : A new polymeric material was prepared from polystyrene beads with N‐substituted amidines and rendered hydrophilic with sulfonate and N‐hydroxyethylsulfamoyl groups. It was synthesized by reacting the p‐chlorosulfonyl polystyrene with ethanolamine followed by the Michael‐like addition of the terminal OH of the polymer (PSEa) to N‐t‐butyl‐N'‐phenylpropenamidine 1 thus leading to the final polymer PSEaAm. Its affinity constant for human α‐thrombin calculated from the Langmuir adsorption isotherms was about 106 M−1, a value comparable to the one estimated for polystyrene modified with L‐arginine methyl ester. This new material was used as stationary phase in affinity chromatography of thrombin confirming a strong and specific interaction between the positively charged amidinium groups and the enzyme at pH = 7.4 and desorption at pH = 10 and high ionic strength. Copyright © 1988 Hüthig & Wepf Verlag