A new macroporous ternary copolymer was synthesized using vinyl acetate (VAC), glycidyl methacrylate (GMA) and allyl methacrylate (AMA) through suspension polymerization with a mixture of n-heptane and butyl acetate as the porogenic agent. The effects of the crosslinking degree, the level of GMA and the porogenic agent mixture and composition on the pore structure of the copolymer and on the properties of the alcoholysed copolymer were investigated. The properties of a typical adsorbent were pore diameter 18.9 nm, pore volume 0.38 ml/g, and specific surface area 80.2 m(2)/g. A hydrophilic polyvinyl alcohol-based matrix was obtained on alcoholysis of the copolymer with the epoxy group unaffected. The alcoholysed copolymer was then attached to a spacer, 6-aminocaproic acid (6-ACA), and finally coupled to 3-aminophenylboronic acid (APBA) as a ligand. The addition reaction between the epoxy group of the matrix and the amino group of 6-ACA was also examined. The ligand density of the prepared affinity adsorbent was 0.865 mmol/g dry resin, which was applied to purify a polysaccharide peptide of Coriolus versicolor (PSP). The optimal conditions for the adsorption of PSP was 0.2 M ammonium acetate (pH 8.2) containing 0.2 M NaCl.