A well-defined amphiphilic graft copolymer (PVDF-g-PAm) was synthesized via surface-initiated atom transfer radical polymerization (SI-ATRP) of acrylamide (Am) from C-F bonds of PVDF as a macro-initiator. PVDF-g-PAm-synthesized copolymer was thoroughly characterized using Fourier-transform infrared spectroscopy (FTIR) and H-1-nuclear magnetic resonance spectroscopy (H-1 NMR). Blend of PVDF and PVDF-g-PAm copolymer was filled with already prepared hierarchical nanostructures of palladium nanoparticles-functionalized graphene oxide (Pd NPs-FGO) to achieve high-performance catalytic nanocomposite membranes. The catalytic activity and reusability of the prepared catalytic membranes for the Suzuki reaction were investigated in a homemade cell. Results revealed that the reactivity and reusability of catalytic membranes containing the hierarchical nanostructures (Pd NPs-FGO) were remarkably improved compared with that of the conventional catalytic membranes containing the unsupported Pd NPs in the membrane matrix. Therefore, the strategy of immobilization of the Pd NPs on the FGO surface is a good approach to minimize the potential Pd NPs loss. The thermal properties, morphology and catalyst content of the prepared catalytic nanocomposite membranes were also studied by means of different techniques such as thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectroscopy (ICP).