Organic waste is generally characterized by high volume-to-weight ratio. Organic waste contaminated with radionuclides may further pose a hazard due to radiolysis and generation of combustible and explosive gases. Thus, minimizing waste volume as well as forming a chemically stable and conditioned matrix are of high importance in the treatment of contaminated polymers. In the present study, the pyrolytic decomposition of the commonly used polyolefins, polypropylene (PP) and high-density polyethylene (HDPE), was explored as a method for waste minimization by obtaining high gaseous and low char and liquid yields. The effects of two aluminosilicate catalysts, Zeolite Y and ZSM-5, and reaction temperature on decomposition efficiency were evaluated based on product conversions and gas composition. Under pyrolytic conditions, PP decomposition resulted in higher decomposition efficiency than HDPE. Over the catalysts, pyrolysis of the polymers over ZSM-5 resulted in higher gas conversions than over Zeolite Y, with a more significant impact on HDPE than PP. Increasing the reaction temperature from 450°C to 525°C also resulted in increased polymer decomposition. However, differences in gas composition, including olefinic to paraffinic ratio and carbon number distribution, support that the catalysts and the temperature impact polymer decomposition by different and opposing mechanisms. This conclusion was further supported by the finding that the decomposition efficiency was not significantly enhanced in the presence of the catalyst at 525°C. Taken together, our study highlights the advantage of using ZSM-5 and optimizing the reaction temperature for treatment of contaminated organic solid waste.