© 2022 The AuthorsThe aim of this study was to investigate the pyrolysis products of polyhydroxyalkanoates (PHAs), polyethylene terephthalate (PET), carbon fiber reinforced composite (CFRC), and block co-polymers (PS-b-P2VP and PS-b-P4VP). The studied PHA samples were produced at temperatures of 15 and 50 oC (PHA15 and PHA50), and commercially obtained from GlasPort Bio (PHAc). Initially, PHA samples were analyzed by nuclear magnetic resonance (NMR) spectroscopy and size exclusion chromatography (SEC) to determine the molecular weight, and structure of the polymers. Thermal techniques such as thermogravimetry (TG) and differential scanning calorimetry (DSC) analyses were performed for PHA, CFRC, and block co-polymers to investigate the degradation temperature range and thermal stability of samples. Fast pyrolysis (500 oC, ∼102 °C s−1) experiments were conducted for all samples in a wire mesh reactor to investigate tar products and char yields. The tar compositions were investigated by gas chromatography–mass spectrometry (GC–MS), and statistical modeling was performed. The char yields of block co-polymers and PHA samples (<2 wt. %) were unequivocally less than that of the PET sample (~10.7 wt. %). All PHA compounds contained a large fraction of ethyl cyclopropane carboxylate (~ 38–58 %), whereas PAH15 and PHA50 additionally showed a large quantity of 2-butenoic acid (~8–12 %). The PHAc sample indicated the presence of considerably high amount of methyl ester (~15 %), butyl citrate (~12.9 %), and tributyl ester (~17 %). The compositional analyses of the liquid fraction of the PET and block co-polymers have shown carcinogenic and toxic properties. Pyrolysis removed matrices in the CRFC composites which is an indication of potential recovery of the original fibers.