Three classes of active halogen compounds were effective in promoting photodegradation of polystyrene, polypropylene, and polyethylene. The classes are arylmethyl halides, phenyl halomethyl ketones, and haloalkenes. The additives were blended with the polymers and fabricated into films which were irradiated 66–200 hr with a 275-watt RS sunlamp. Photo-oxidation, as determined by IR spectroscopy, was used as a measure of photodegradation. The relationship between the structure of the additive and its effectiveness as a photoinitiator within each of the three classes of compounds is discussed. In general, photoactivated polystyrene was degraded the most, followed by polypropylene and then polyethylene. Viscosity measurements on irradiated polystyrene containing the additives showed significantly greater molecular weight loss than a polystyrene control.