Films of poly(acrylonitrile-co-2,3-dimethyl-1,3-butadiene) were exposed to singlet oxygen. The extent of polymer oxygenation was monitored for singlet oxygen generated (1) within the polymer film and (2) at the polymer surface in an aqueous medium. When singlet oxygen is generated within the film, oxygenation of the polymer is pronounced and extensive. When singlet oxygen is generated at the polymer surface, oxygenation reactions are limited to the surface. The data suggest that the initial oxygenation reactions at the film surface passivate the polymer against further reaction with singlet oxygen and, hence, also minimize the progressively detrimental effects of secondary reactions. These results indicate that one should exercise restraint when implicating singlet oxygen as a reactive species in some processes of polymer oxygenation.