An affinity adsorbent, Cibacron Blue 3GA immobilized magnetic polyvinyl alcohol (PVA) microsphereswas used for bilirubin removal taking the advantage of easy separation of magnetic sorbent from the biosystem.Fe3 O4 superparamagnetic particles was synthesized with hydrothermal reaction of ferrous chloride (FeCl2) and ferricchloride (FeCl3). Such magnetic particles are then encapsulated in biocompatible PVA to form magnetic polymermicrospheres sized from 2 to 15 nm with hydroxyl groups on its surface. Cibacron Blue 3GA, a dye-ligand, wascovalently coupled with the polyvinyl alcohol through the nucleophilic reaction between the chloride of its triazinering and the hydroxyl groups of PVA molecules under alkaline condition. The affinity adsorbent carried 21.1 μmolCibacron Blue 3GA per gram magnetic polymer microspheres was used to remove unconjugated and conjugatedbilirubin from the solution which was composed of bilirubin or bilirubin and protein. After the adsorption, theadsorbent loaded with bilirubin was removed easily in the magnetic field.