Hyperbilirubinemia, caused by the disorders in bilirubin metabolism, could result in neurotoxicity, permanent brain damage and even death. As one of effective bilirubin removal technologies from blood, hemoperfusion had attracted much attention. However, the development of bilirubin adsorbents used in hemoperfusion with excellent adsorption capacity and hemocompatibility still faced great challenges. In this work, the cationic hydrogel was prepared by the photo-initiated polymerization of biodegradable poly(ester amine) (PEA) based on PLLA and low molecular weight PEI1800. The PEA hydrogel had favorable swelling behavior and bilirubin adsorption capacity, and the bilirubin adsorption amount could reach up to 374.43 mg/g. The effects of pH value, ionic strength and human serum albumin (HSA) were also studied. Besides, the results of hemolytic test indicated that PEA hydrogel had favorable hemocompatibility. Based on these results, the prepared PEA hydrogel would be quite hopeful as an effective adsorbent for bilirubin removal from blood.