Hyperbilirubinemia is one of most severe clinical diseases, which is caused by the accumulation of unconjugated bilirubin. Electrospun nanofiber membranes used as highly efficient bilirubin adsorbents have been applied to remove the extra bilirubin in hemoperfusion for their high surface area and easy functionalized properties. In this work, Lysine (Lys) grafted polyacrylonitrile (PAN) electrospun nanofiber membranes doped with organic Hectorite (OHec) ([email protected]) have been fabricated via a series of modified process, including pore forming, alkaline hydrolysis and grafting reaction. The obtained [email protected] nanofiber membranes have been analyzed in detail and investigated the adsorption capacity for bilirubin. Compared with original PNA membranes, [email protected] nanofiber membranes show an excellent bilirubin adsorption capacity and more stable rejection rate of bovine serum albumin (BSA). The maximum adsorption capacity of [email protected] membranes for bilirubin is 64 mg/g, the adsorption process of [email protected] membranes matched the Langmuir model well. In addition, dynamic adsorption reveals that the adsorption equilibrium time of [email protected] membranes is about 2 h. Significantly, [email protected] membranes have excellent biocompatibility and hemocompatibility. This study demonstrates that the novel [email protected] membranes may provide a new way to treat hyperbilirubinemia.