In this work, the ATRP polymerization technique was first utilized for controlled grafting of methyl methacrylate monomers from a Poly(vinylidene fluoride) (PVDF) backbone with a predefined molecular weight and narrow molecular weight distribution. After the successful formation of the copolymer, different amounts of the prepared PMMA‐g‐PVDF copolymer along with TiO2 nanoparticles were then employed for the fabrication of PVDF mixed matrix membranes (MMMs). The separation performance of the fabricated membranes was evaluated in rejection of different dyes including Methyl Green (MG), Rhodamine B (RDB), Crystal Violet (CV), and Methylene Blue (MB) from aqueous solutions. It was observed that a high rejection ability (99.6%, 99.1%, 98.9%, and 96.1% for MG, RDB, CV, and MB), a good permeate Flux of 8.35 L/m2 h along with an outstanding antifouling performance were provided by the membrane with 0.4% PVDF‐PMMA and 0.2%TiO2.