We report the synthesis and characterization of well-defined homo- and diblock copolymers containing poly(furfuryl glycidyl ether) (PFGE) via living anionic ring-opening polymerization using different initiators. The obtained materials were characterized by SEC, MALDI-TOF MS, and H-1 NMR spectroscopy and molar masses of up to 9400 g/mol were obtained for PFGE homopolymers. If the amphiphilic diblock copolymer PEG-block-PFGE was dissolved in water, micelles with a PFGE core and a PEG corona were formed. Hereby, the hydrophobic PFGE core domains were used for the incorporation of a suitable bismaleimide and heating to 60 degrees C induced the crosslinking of the micellar core via Diels-Alder chemistry. This process was further shown to be reversible. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 4958-4965, 2012