A well-defined amphiphilic block copolymer, poly (ethylene oxide)-b-(poly (furfuryl methacrylate) (PEO-b-PFMA) was prepared by single electron transfer living radical polymerization using tris(dimethylamino)ethyl amine (Me6TREN) as a ligand. The block copolymer formed sub-100nm micelles in water with PEO as a shell and PFMA as a core. Diels-Alder click type reaction was employed to form core-crosslinked micelles using a diselenide-containing crosslinker without any catalyst. The block copolymer and micelles were characterized by gel permeation chromatography, nuclear magnetic resonance, Fourier-transform infrared spectroscopy, dynamic light scattering analysis and transmission electron microscopy. The stability of core-crosslinked micelles under reductive-oxidative condition was also investigated. The diselenide crosslinked micelles displayed good stability against extensive dilution but decomposed under the presence of hydrogen peroxide or glutathione. The redox responsive core-crosslinked micelles can be a promising carrier for drug delivery applications.