The synthesis of a polyethylene (PE) gel containing self-incarcerated palladium(0) nanoparticles is described. The PE gel matrix without any special functionality was synthesized by one-pot chain walking copolymerization of ethylene and 1,6-hexanediol diacrylate facilitated by a Pd–diimine complex (1). The Pd(II) species from 1 were immobilized in situ onto the gel matrix and further reduced to Pd(0) nanoparticles as a result of catalyst 1 deactivation during polymerization and methanol (a reducer) washing in the polymer purification process. The resulting Pd-containing PE gel (2) is shown to be a high-performance and facilely reusable heterogeneous catalyst for the Heck and Suzuki coupling reactions of iodobenzene or aryl bromides. An average TOF of 460 h
1 was achieved with an average 0.57 ppm Pd leaching in each cycle of the Heck reaction of iodobenzene when the PE gel 2 was recycled 10 times. A maximum TOF of 3.33  104 h
1 was reached and less than 0.64 ppm of Pd was leached in the Suzuki reactions of aryl bromides with water as solvent.