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This work describes the development of analytical workflows based on pyrolysis coupled with gas chromatography-mass spectrometry (Pyr-GC/MS) for the qualitative and quantitative analysis of 12 of the most common plastic polymers in environmental samples. The most suitable characteristic pyrolyzate compounds and respective indicator ions were selected for each polymer in order to obtain the most appropriate response for analytical purposes. Additionally, commercial pyrolyzates and polymers libraries were used to confirm the identity of the detected microplastics. The method was validated, showing a good linearity for all the plastic polymers (R2 > 0.97) and limits of detection between 0.1 (polyurethane) to 9.1 µg (polyethylene). The developed methodology was successfully applied for the analysis of plastic polymers in environmental microplastic samples collected in three Mediterranean beaches (NE Spain). • Fast and reproducible Pyr-GC/MS method for the analysis of the 12 most common plastic polymers in a single GC/MS run • Straightforward analytical workflows using pyrolyzates and polymers libraries enable a fast identification and quantification of microplastics in environmental samples