Two nonconventional extraction techniques, microwave assisted extraction (MAE) and ultrasonication, were used to extract degradation products from polyolefins with enhanced degradability. High-density polyethylene/polypropylene blends with two different biodegradable additives (a granular starch/iron oxide mixture and Mater-Bi AF05H) were subjected to outdoor soil burial tests and removed at different periods of time between 0 and 21 months. The extracted products were analyzed by gas chromatography mass spectrometry (GC-MS). Ultrasonication was found to be a more suitable technique than MAE because of better reproducibility. In addition, higher amounts of certain products (e.g., carboxylic acids) were extracted by ultrasonication than by MAE. The degradation products extracted from the two blends were basically a homologous series of alkanes, alkenes, carboxylic acids, and alcohols. The amount of hydrocarbons (saturated and unsaturated) and alcohols remained basically the same as the degradation times increased. However, carboxylic acids tended to decrease slightly with the exposure time. Their concentration remained practically unchanged until 12 months of soil burial when a more significant decrease was noted. The quantitative analysis of the degradation products revealed for both samples a decrease in the amount of carboxylic acids with the exposure time, although the trend was different according to the additive used in each sample. For blends with Mater-Bi the amount of carboxylic acids was at a minimum after 12-month exposure in soil, which coincided with a minimum in the molecular weight distribution. After blends with granular starch/iron oxide were exposed to 3 months in soil, tetradecanoic acid was no longer detectable and the amount of hexadecanoic and octadecanoic acids decreased significantly. Solid-phase microextraction, a solvent-free extraction technique, was used to extract the degradation products that could have migrated to the soil from blends with Mater-Bi. Small amounts of tetradecanoic acid and dodecanol were identified by GC-MS in the soil surrounding the sample. The degradation patterns observed here correlate with our previous results from mechanical and morphological characterization of these samples.