Abstract Modified polyacrylamide brushes including phosphinite functionality grafted onto silica supported Pd nanoparticles were synthesized via RAFT polymerization technique in a controlled manner with elucidated graft density and chain length. Proper activity of the catalyst was indicated in the Mizoroki–Heck coupling reaction of various haloarenes with olefins. Different aryl iodides with electron rich and electron deficient substituent and also ortho and heterocyclic substrate showed good reactivity to generate the corresponding coupled products in good to excellent yields using low Pd loading. The turnover number (TON) for this catalyst can be reduced up to 9.5 × 103. Simple filtration, appropriate reusability and negligible palladium leaching of this catalyst are among other advantages.