Poly (vinyl chloride) /poly (acrylonitrile) (PVC/PAN) hollow fiber membrane was prepared by phase inversion method and it was hydrolyzed in different NaOH solution concentration. After hydrolysis modified, the change of surface characteristic of the PVC/PAN hollow ﬁber membrane was described by Fourier transform infrared attenuated total reﬂection spectroscopy (FTIR-ATR) and water contact angle. Morphological structures of membranes were observed by field-emission scanning electron microscope (FESEM). Protein ﬁltration was employed to evaluate the antifouling performance of the membrane. All these results demonstrated that PVC/PAN hollow ﬁber membrane modiﬁed by hydrolysis showed high permeation ﬂux, good hydrophilicity and antifouling.