The present disclosure provides thermosetting biophotonic compositions and methods useful in phototherapy. In particular, the thermosetting biophotonic compositions of the present disclosure include block copolymer and at least one chromophore solubilized in the block copolymer. The thermosetting biophotonic compositions and the methods of the present disclosure are useful for promoting wound healing and skin rejuvenation, as well as treating acne and various other skin disorders.