The polyvinylidene fluoride (PVDF) as a matrix material was prepared for a bilirubin⁃adsorbed membrane. Firstly, PVDF microfiltration membrane was prepared by vapor⁃induced phase inversion method. The effects of polymer concentration, solvent and additive type on membrane properties and structure were investigated. It is found that PVDF microfiltration membrane has excellent performance and morphology with the PVDF concentration in the casting solution of 7%~8% in quality. When blend solvent of acetone and N, N⁃dimethylformamide and the additive of glycerol were selected, pure water flux is higher than others. Polyethyleneimine was further coated on the matrix to prepare a modified PVDF membrane. The results showed that the modified PVDF membrane had certain serum bilirubin removal ability.