In this paper, the amount of polyethylene (PE) contained in complex biodegradable polymer blends and in carrier bags claimed to be compostable was determined by thermogravimetry analysis (TGA) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). To validate the method, polymer blends based on polylactide (PLA), poly(butylene adipate-. co-butylene terephthalate) 53/47 (PBAT), native starch (NS), and calcium carbonate, with known amount of PE ranging from 0 to 10%, were prepared by melt mixing. Py-GC/MS parameters were optimized. In the first step at 400. °C, pyrolysis products originated from thermal cracking of PLA, NS and PBAT were detected. In the second step carried out at 500. °C, triplet peaks characteristic for PE, consisting of α,ω-dienes, α-alkenes and n-alkanes, were revealed together with some signals related to PBAT. TGA under nitrogen atmosphere was used to determine the amount of PE in the blends. An overestimation of about 1.2%, constant for all the blends, was revealed. The overestimation was attributed to the partial overlapping of one of the steps of degradation of the commercial PBAT and that of PE. Additionally, the analytical approach was applied in the characterization of carrier bags claimed to be compostable, recovered directly from the market. The correct determination of the composition of these biodegradable blends is important and crucial to comply with the compostability standard EN 13432-2000. According to this standard, each significant organic constituent of the packaging material must be biodegradable. "Significant" means any constituent present in more than 1% of dry weight of that material. This implies that maximum allowed PE concentration that can be detected in a compostable blend is 1%. In two commercial carrier bags, TGA revealed a component with a degradation temperature of about 455. °C corresponding to that of PE. The relative weight loss percentages of these two carrier bags have been estimated 7.6 and 14%. Optimization of the Py-GC/MS conditions allowed identifying its chemical structure. In fact, the Py-GC/MS at 500. °C provided a pyrogram that was a fingerprint for PE with triplets corresponding to linear chains of α,ω-dienes, α-alkenes and n-alkanes with chain lengths in the range of 9-36 C atoms. Overall, the results show that the combination of TGA and Py-GC/MS can be applied with practical implications.