Well-defined azlactone-functionalized polymers have emerged as highly valuable precursors for the synthesis of (bio)molecules-conjugated materials. The development of polymerization process working at moderate temperature or ambient temperature and without use of metal catalysts or odorous agents for the synthesis of azlactone-functionalized polymers would be attractive, particularly in biomedical applications. In the present study, we have successfully copolymerized 2-vinyl-4,4-dimethylazlactone (VDM) and methacrylate monomers such as methyl methacrylate and poly(ethylene glycol) methyl ether methacrylate (mPEGMA) by photoinduced reversible complexed mediated polymerization (photo-RCMP). The polymerization was conducted at a wavelength of 365 nm and was well controlled with an initial ratio of VDM as high as of 20 mol%. The copolymer molecular weight and its dispersity (Ð < 1.3) was well controlled during the whole process and the system was perfectly a photo-switchable “on/off” system with no polymerization took place when the system was not irradiated. In addition, the ability of the resulting amine-reactive copolymer to be engaged in post-polymerization modifications was demonstrated using furfurylamine and l-carnosine.