Poly(epsilon-caprolactone) (PCL)-based thermoreversible networks with self-healing properties were prepared through DielsAlder (DA) and retro-DA reactions. Bis- or Tris-maleimide compounds and a series of copolymer(caprolactone-diene) PCLXFY (X: degree of polymerization and Y: furan-average functionality) with Y between 2.4 and 4.9 were used. The successive sequences of formation and dissociation of polycaprolactone networks via DA and retro-DA reactions were observed repeatedly by dynamic mechanical analyses (DMA) and their gel-temperatures determined. The cross-linking densities, thermal properties, and thermal reversibility of the PCLXFY/multimaleimide polymers have been modulated by the structure and functionalities of the used diene and dienophile moieties. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013