Abstract: Allyl terminated poly(dimethylacrylamide) were synthesized via atom transfer radical polymeri zation, which was modified to be azide terminated poly(dimethylacrylamide) and reacted with alkyne terminated poly(dimethyl siloxanes) to get tri-block copolymers via click chemistry. The chemical structures were characterized by 1H-NMR, FT-IR and GPC. Results showed that the PDMAAm homopolymer was synthesized with controlled molecular weight and low polydispersities, the click chemistry was an efficient and easy method to combine the thermodynamically incompatible hydrophilic PDMAAm segments and hydrophobic PDMS segments into block polymer combination PDMAAm-PDMS-PDMAAm.