A new synthetic approach to prepare Ag nanoparticles protected side-chain liquid crystalline (LC) azobenzene polymers was reported. It is based on the reduction of silver ions in presence of a LC polymer polymerized by RAFT. The formation of Ag colloidal nanoparticles was confirmed by TEM and UV analysis. At the same time, according to the results of DSC, XPS, and FTIR spectra, Ag nanoparticles were protected by the side-chain LC azobenzene polymers through surface attachment interactions between thiol groups and Ag. The out-plane orientation of side-chain LC is confirmed by surface-enhanced Raman spectra analysis and scanning near-field optical microscope, resulting from the large electromagnetic field arising from the excitation of surface plasmon polariton of Ag nanoparticles. (c) 2007 Wiley Periodicals, Inc.