Gel networks could be achieved via the photocycloaddition and cross-linking of olefin moieties in branched polymers. The formed cyclobutane unit made the bulky gel photoreversible, which shows potential for promising applications in self-healing, drug release and extracellular matrices. Related research on gel networks formed via [2+2] photocycloaddition was retraced and the potential utilization of visible light catalysis was also conceived.