A functionalized L-glutamate N-carboxyanhydride monomer containing a cinnamyl moiety, γ-cinnamyl-L-glutamate N-carboxyanhydride (CLG-NCA), was prepared. Ring-opening polymerization (ROP) of CLG-NCA initiated by n-hexylamine and amino-terminated poly(ethylene glycol) (mPEG-NH₂) was successfully performed with controlled polymer molecular weight and molecular weight distribution. The structures of the obtained monomer and polymers were confirmed by ¹H NMR, ¹³C NMR and FTIR. The block copolymer mPEG-b-PCLG could self-assemble into micelles in aqueous solution which consist of a hydrophobic PCLG core and a hydrophilic mPEG shell. Under UV-irradiation at 254 nm, the photo-cross-linking process of the cinnamyl-carrying block copolymer micelles was tracked by UV-Vis spectra, ¹H NMR, dynamic light scattering (DLS) and transmission electron microscopy (TEM). In vitro MTT assay demonstrated that the micelles were biocompatible to L929 cells. Paclitaxel was loaded into the micelles as a model drug. The in vitro paclitaxel release behaviors indicated that cross-linking of the micelle cores results in a slow drug release in comparison with the non-cross-linked micelles. These results indicated that the photo cross-linked mPEG-b-PCLG micelles can be used as drug carriers for intelligent drug delivery.