The application of well-defined poly(furfuryl glycidyl ether) (PFGE) homopolymers and poly(ethylene oxide)-b-poly(furfuryl glycidyl ether) (PEO-b-PFGE) block copolymers synthesized by living anionic polymerization as self-healing materials is demonstrated. This is achieved by thermo-reversible network formation via (retro) Diels-Alder chemistry between the furan groups in the side-chain of the PFGE segments and a bifunctional maleimide crosslinker within drop-cast polymer films. The process is studied in detail by differential scanning calorimetry (DSC), depth-sensing indentation, and profilometry. It is shown that such materials are capable of healing complex scratch patterns, also multiple times. Furthermore, microphase separation within PEO-b-PFGE block copolymer films is indicated by small angle X-ray scattering (lamellar morphology with a domain spacing of approximately 19 nm), differential scanning calorimetry, and contact angle measurements.