To enhance the anti-fouling and separating properties of polyvinylidene fluoride (PVDF) membranes, an amphiphilic copolymer of methyl methacrylate and 2-acrylamido-2-methylpropane sulfonic acid, poly(MMA-co-AMPS), was designed and synthesized. Through a phase-inversion process, the poly(MMA-co-AMPS) were fully dispersed in the PVDF membrane. The properties of membrane including the surface and cross-section morphology, surface wettability and fouling resistance under different pH solutions were investigated. Compared to the unmodified PVDF membranes, the contact angles of modified PVDF membranes decreased from 80.6° to 71.6°, and the pure water flux increased from 54 to 71 L·m−2·h−1. In addition, the hybrid PVDF membrane containing 0.5 wt% copolymers demonstrated an larger permeability, better fouling resistance and higher recovery ratio via pure water backlashing, when it was compared with the other blend membranes, and the virgin one in the cyclic test of anti-fouling. The modified membranes with the copolymers possessed an outstanding performance and may be used for further water treatment applications.