This study demonstrated the feasibility of polymer brushes-modified plate substrate as template to construct multilayer thin films via layer-by-layer hydrogen bonded assembly. The anchored chains via controlled surface-initiated atom transfer radical polymerization (SI-ATRP). The anchored
poly(4-vinylpyridine) brushes functions as a multivalent H-acceptor to regulate the following hydrogen bonded assembly with H-donors to construct multilayer thin films via layer-by-layer deposition technique. The growth mechanism and film natures of multilayer films mediated by hydrogen bonded
assembly from a polymer brushes-grafted surface were fully investigated.