Functional terpolymer of poly(methyl methacrylate-2-hydroxyethyl methacrylate-acrylic acid) (P(MMA–HEMA–AA)) was synthesized via a radical polymerization method. The terpolymer could be directly blended with poly(vinylidene fluoride) (PVDF) to prepare the microfiltration (MF) membranes via phase separate process. The synthesized polymers were characterized by Fourier transform infrared (FTIR), the nuclear magnetic resonance proton spectra ( 1 H NMR). The membrane had the typical asymmetric structure and the hydrophilic side chains tended to aggregate on the membrane surface. The surface enrichment of amphiphilic copolymer and morphology of MF membranes were characterized by Fourier transform infrared attenuated total reflection spectroscopy (FTIR–ATR) and scanning electron microscopy (SEM). The contact angle (CA) and water uptake were also tested to assess the hydrophilicity and wetting characteristics of the polymer surface. The water filtration properties were measured. It was found the modified membranes showed excellent pH-sensitivity and pH-reversibility behavior. Furthermore, the hydrophilicity of the blended membranes increased, and the membranes showed good protein antifouling property.