In summary, broadband white LED irradiation (450 nm-800 nm) and blue led (400 nm) in combination with EY, ErB dyes or PPT in the novel photodegradation system is established to overcome the requirement of heat and metal catalysts. Two types of halogen-containing PMMA derivatives have been synthesized to detect optimal conditions for the subsequent degradation process. P(MMA-co-MCA) was degraded to outstandingly low molecular weights using visible light in the presence of organo photocatalysts. Temporal control and the kinetics of the novel degradation process were investigated by taking aliquot samples from reaction media and performing GPC analyses. The thermal properties of the copolymers were also examined by DSC and TGA to outline their potential as a substitute for PMMA in commercial use.