Polyurethanes (PUR) are a group of polymers synthesized from different diisocyanate and polyol monomers resulting in a countless number of possible structures. However, the large market demand, and the variety of application fields justify the inclusion of PUR in microplastic (MP) investigation. This study aimed at providing comprehensive information on PUR within MP analysis by pyrolysis–gas chromatography-mass spectrometry to clarify whether (i) it is possible to make a reliable statement on the PUR content of environmental samples based on a few pyrolysis products and (ii) which restrictions are required in this context. PUR were managed as subclasses defined by the diisocyanates employed for polymer synthesis. Methylene diphenyl diisocyanate (MDI)- and toluene diisocyanate (TDI)-based PUR were selected as subclasses of greatest relevance. Different PUR were pyrolyzed directly and under thermochemolytic conditions with tetramethylammonium hydroxide (TMAH). Distinct pyrolytic indicators were identified. The study supported that the use of TMAH greatly reduced the interactions of pyrolytic MP analytes with the remaining organic matrix of environmental samples and the associated negative effects on analytical results. Improvements of chromatographic behavior of PUR was evidenced. Regressions (1–20 µg) showed good correlations and parallelism tests underlined that quantitation behavior of different MDI-PUR could be represented by the calibration of just one representative with sufficient accuracy, entailing a good estimation of the entire subclass if thermochemolysis were used. The method was exemplary applied to road dusts and spider webs sampled around a plastic processing plant to evaluate the environmental spread of PUR in an urban context. The environmental occurrence of MDI-PUR as MP was highly influenced by the proximity to a potential source, while TDI markers were not observed.Graphical AbstractSupplementary InformationThe online version contains supplementary material available at 10.1007/s00216-023-04580-3.