© 2019 American Chemical Society. Luminescent solar concentrators (LSCs) are a promising solar energy technology for reducing architectural barriers to the integration of photovoltaic systems into the built environment. In this work, the first demonstration of thin-film LSCs based on a thermally reversible cross-linked host polymer is presented. This smart material is obtained via a dynamic-chemistry approach based on the Diels-Alder (DA) reaction between a furan-functionalized acrylic copolymer and an aliphatic bismaleimide to obtain optically clear, cross-linked systems capable of healing mechanical damage upon heat treatment. By carefully tuning the concentration of a perylene-based luminophore dopant, an optical efficiency as high as 4.9% can be achieved with this DA-based LSC. In addition, full recovery of device efficiency is demonstrated after complete thermal healing of mechanically induced surface damages as a result of the embedded DA functionality. The approach presented here paves the way to the development of highly efficient multifunctional thermoresponsive smart LSC systems.