Polyesters labelled as bio-based or compostable are increasingly common among the ‘bioplastics’ in use as food contact materials (FCM). The knowledge of material composition is mandatory to predict potential leachable oligomers as well as to partly evaluate the correctness of the label ‘bioplastic’, which is used for promotional purposes. The composition of (bio)polyesters can be determined by alkaline hydrolysis of the entire material and subsequent analysis of the monomers via high-performance liquid chromatography with diode array detection and GC-MS detection. Thirty-three frequently used monomers (polycarboxylic acids, hydroxy carboxylic acids, polyols) including highly polar monomers such as lactic acid were analysed with detection limits below 10 g/kg of the material. Lactic acid enantiomer elucidation was performed using an enzyme assay. The content of non-hydrolysable residue was determined gravimetrically after hydrolysis, and the inorganic residue after washing. The composition of 12 polyesters mostly in food contact, labelled as bio-based or compostable and sampled from the market was elucidated recovering 92–101% of the total mass by summing up the determined monomers and non-polyester contents. Seven different monomers were detected in the 12 samples (up to four different monomers per sample), lactic acid being the most common (9 samples) with contents ranging from a minor component (about 11 mol%) up to the only monomer found in the material. The ratio of d- to l-lactic acid ranged from 0.3:99.7 to 4.7:95.3 (w/w). The non-hydrolysable (in)organic residue was quantified in amounts of up to 390 g/kg. Overall, the presented analytical protocol is a fundamental tool helping both to verify the appropriateness of labelling as biopolyesters as well as to predict potential leachables such as oligomers during an FCM risk assessment.