Well-defined methacrylate based amphiphilic block copolymers (BCs) used as additives to fabricate poly(vinylidene fluoride) (PVDF) UF membranes, where the amphiphilic BC additives hydrophilically altered PVDF with PPEGMA block segment by strong interaction with the other PMMA block segment, which reduced water resistance to the PVDF polymer solution during phase separation. FT-IR and XPS studies showed carbonyl groups of BCs in the PVDF membranes. Obtained membranes showed porous surface layer and finger-like pore structures on the sublayers, of which sizes were increased with the increase of BC contents. Obtained membranes showed MWCO with 100K PEO and the best water flux was achieved in the PVDF membrane with BC/LiCl additive and improved the anti-fouling property for BSA protein.