Oxidative stress is highly prevalent in maintenance hemodialysis patients and increases the risk of cardiovascular morbidity and mortality. Silibinin (SLB) is a plant extract with excellent antioxidant effects. The polymer of polysulfone (PSF) grafted SLB (PSF-g-SLB) was synthesized using a two-step approach, and the PSF-g-SLB membrane, a porogen-additive-free blood purification membranes made up of simply the polymer and solvent, was fabricated via the nonsolvent induced phase separation method. The results showed that, with increasing the grafting rate of PSF-g-SLB, the hydrophilicity, antioxidant properties, and the stability of free radical scavenging rate of the PSF-g-SLB membranes were improved. Furthermore, platelet-erythrocyte adhesion and hemolysis rate were decreased, and coagulation time was prolonged. The PSF-g-SLB membrane exhibits significant potential for being compatible with hemocompatibility, biocompatibility, and antioxidant properties. Therefore, the application of PSF-g-SLB membranes could alleviate oxidative stress in patients during hemodialysis.