The environmental persistence of post-consumer plastics remains a critical challenge due to their chemical stability, the presence of additives, and prior environmental weathering. This study evaluates the partial biodegradation and chemical transformation of post-consumer low-density polyethylene (LDPE) and expanded polystyrene (EPS) by Tenebrio molitor larvae under uncontrolled environmental conditions. Four diets were tested, including LDPE+S and EPS+S (polymers supplemented with wheat bran), to assess the influence of a co-substrate on larval performance and polymer transformation. Fourier-transform infrared spectroscopy (FTIR) revealed the emergence of oxygen-containing functional groups (–OH and C=O) in the frass, which were absent or negligible in pristine materials, indicating oxidative modification of the polymer matrix. Gel permeation chromatography (GPC) revealed pronounced reductions in number-average molecular weight (Mn) and increased polydispersity for EPS-derived fractions, consistent with heterogeneous chain scission and partial depolymerization. For LDPE, GPC evidenced the formation of THF-soluble, low-molecular-weight polymer-derived fragments, indicating fragmentation despite the inability to quantify pristine LDPE due to its insolubility in the mobile phase. Gas chromatography–mass spectrometry (GC–MS) identified aromatic hydrocarbons, phthalate esters, organosiloxanes, and fatty acid derivatives, reflecting both degradation intermediates and migrated additives from post-consumer plastics. Together, these results provide integrated evidence that Tenebrio molitor can induce chemical transformation of post-consumer LDPE and EPS under non-controlled environmental conditions, offering mechanistic insight into a biologically mediated degradation pathway that is directly relevant to realistic plastic waste scenarios.