Double hydrophilicblock copolymers mPEG-b-PDMAEMA were synthesized by Atom Transfer Radical Polymerization. With copolymer as substrate, water as medium, the silver nitrate as precursor, the composite particles of nano silver/ mPEG-b-PDMAEMA were prepared by microwave radiation. FTIR and 1HNMR results showed that the target copolymer was prepared by Atom Transfer Radical Polymerization. X-rays and UV-vis results showed that silver nanoparticles had good face-centered cubic crystal structures. TEM pictures showed that nano silver attached on the surface of copolymer and the composite materials were spherical particles. The mechanism of silver ion reduced to nanosilver particles catalyzed by PDMAEMA under microwave was discussed.Cited