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In this study, Polyvinylidene fluoride (PVDF) hollow fiber hemodialysis membranes were prepared by non-solvent induced phase separation (NIPS) with compound addtive. The compound additive was made with polyvinyl pyrrolidone (PVP) and Poly ethylene glycol (PEG). The results showed that the modified PVDF membrane had better separation performance than virgin PVDF membrane. The UF flux of modified PVDF membrane can reach 684 L·h−1·m−2 and lysozyme (LZM) passage is 72.6% while virgin PVDF membrane is 313 L·h−1·m−2 and 53.2%. At the same time, the biocompatibility of PVDF membranes was also improved. Compared with commercial polysulfone hemodialysis membrane (Fresenius F60S membrane), the modified PVDF membrane had better mechanical and separation performance. The stress and tensile elongation of modified PVDF membrane was 0.94 MPa and 352% while Fresenius F60S membrane was 0.79 MPa and 59%. The LZM passage reached 72.6% while Fresenius F60S membrane was 54.4%. It was proven that the modified PVDF membrane showed better hydrophilicity, antithrombogenicity, less BSA adsorption, and lower hemolytic ratio and adhesion of platelets. Water contact angle and BSA adsorption of the modified PVDF membrane are 38° and 45 mg/m2 while Fresenius F60S membrane are 64° and 235 mg/m2. Prothrombin time (PT) and activated partial thromboplastin time (APTT) of the modified PVDF membrane are 56.5 s and 25.8 s while Fresenius F60S membrane is 35.7 s and 16.6 s. However, further biocompatibility evaluation is needed to obtain a more comprehensive conclusion.