Isocyanic acid (ICA) in vapour phase has been reported to be of unstable nature, making the occupational hygienic relevance of ICA questionable. The stability of pure ICA in clean air at different humidity conditions was investigated by Fourier transform-infrared spectrometric (FT-IR) measurements. Furthermore, the stability of ICA in a complex atmosphere representative thermal degradation hot-work procedures were examined by performing parallel measurements by proton transfer reaction-mass spectrometric (PTR-MS) instrumentation and off-line denuder air sampling using di-n-butylamine (as a derivatization agent prior to liquid chromatography mass spectrometric (LC-MS) determination). The apparent half-life of ICA in pure ICA atmospheres was 16 to 4 hours at absolute humidity (AH) in the range 4.2 to 14.6 g m⁻³, respectively. In a complex atmosphere at an initial AH of 9.6 g m⁻³ the apparent half-life of ICA was 8 hours, as measured with the denuder method. Thus, thermally formed ICA is to be considered as a potential occupational hazard with regard to inhalation. The generation pattern of ICA formed during controlled gradient (100–540 °C) thermal decomposition of different polymers in the presence of air was examined by parallel PTR-MS and denuder air sampling. According to measurement by denuder sampling ICA was the dominant aliphatic isocyanate formed during the thermal decomposition of all polymers. The real-time measurements of the decomposed polymers revealed different ICA generation patterns, with initial appearance of thermally released ICA in the temperature range 200–260 °C. The PTR-MS ICA measurements was however affected by mass overlap from other decomposition products at m/z 44, illustrated by a [ICA]_Denuder/[ICA]_PTR-MS ratio ranging from 0.04 to 0.90. These findings limits the potential use of PTR-MS for real time measurements of thermally released ICA in field, suggesting parallel sampling with short-term sequential off-line methodology.