Poly(2-hydroxyethyl methacrylate) (PHEMA) brushes were grown from flat silicon wafers with surface-tethered alpha-bromoester initiator via atom transfer radical polymerization (ATRP) in aqueous media at ambient temperature first. Kinetics studies revealed an approximate linear increase in thickness with reaction time, indicating that the polymerization process owned some "living" character. Then a kind of polymer-metal complexes (PMCs) were obtained after the introduction of Cu2+ cations into the PHEMA brushes by the complexing bond between Cu2+ cations and the hydroxyl groups in PHEMA brushes. Finally, the Cu2+ cations in PMCs were reduced by NaBH4 and a kind of PHEMA brushes containing metal nanoparticles of Cu-0 was formed.