Here we report a type of N-heterocyclic carbene (NHC)- and phosphine-chelated palladium catalysts with poly(ethylene glycol) (PEG) chain for Suzuki-Miyaura cross-coupling reactions. 1-(2-Diphenylphosphinoferrocenyl)-ethyl-3-imidazolium iodides conjugated with MeO-PEG(400) and MeO-PEG(750), respectively, have been synthesized and characterized. It was demonstrated that the salts bearing with PEG chain could act as NHC precursors successfully under the catalytic condition to form NHC-supported palladium complexes joined by phosphine. The formed palladium complexes are highly efficient for Suzuki-Miyaura coupling of aryl bromides with phenylboronic acid at the palladium loading of 0.1 mol% in both organic and aqueous solvents.