The effect of oxidizers on the microwave-assisted oxidative degradation kinetics of poly(alkyl acrylates), namely, poly(methyl acrylate) (PMA), poly(ethyl acrylate) (PEA), and poly(butyl acrylate) (PBA), was studied. The molecular weight distributions were measured by gel permeation chromatography, and continuous distribution kinetic models were used to determine the degradation rate coefficients. The effect of alkyl group substituents on the microwave-assisted oxidative degradation of poly(alkyl acrylates) was also investigated. The degradation rate of poly(alkyl acrylates) decreased with an increase in the number of carbon atoms of the alkyl substituents and thus followed the order PMA > PEA > PBA, while the activation energy increased with the length of alkyl group substituents. The rate coefficients of hydrogen abstraction and oxidative random chain scission were found to be independent of the oxidizer and dependent only on the nature of the polymer. The differences in the overall degradation rate of poly(ethyl acrylate) in the presence of different oxidizing agents were only dependent on the rate of oxidizer dissociation. This is the first study that shows that the degradation rate of the polymer in the presence of any oxidizer can be predicted by knowing only the thermal dissociation rate constant values of the oxidizer, which can be easily obtained from existing literature. © 2008 American Chemical Society.