Polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared via thermally induced phase separation (TIPS) method by using diphenyl ketone (DPK)-N, N-dimethyl acetamide (DMAc) as diluent and phenolphthalein polyethersulfone (PES-C) as additive. The structure of membrane was observed through SEM and pure water flux, sewage flux, COD and NH4+-N content of MBR effluent were also investigated. A thinner skin layer and porous support layer were formed when 2% PES-C was added into casting solution. Compared with PVDF membrane, the pure water flux of membrane prepared with 2% PES-C addition increased by 60 percent and the sewage flux increased by 37.8 percent, well COD removal ratio of the effluent increased by 3.32 percent and NH4+-N removal ratio increased by 2.2 percent and also the effluent of the membrane came up the discharge standard.