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Dermal exposure to sensitizers such as diisocyanate have been described to promote the development of asthma in later stages when respiratory occupational exposure occurs. Therefore, we developed a reliable, sensitive and validated methodology based on dermal patches to assess skin exposure to diisocyanates.An UPLC-Unispray-MS/MS method was established and validated in order to reach very low levels of detection. Custom-made dermal patches were developed in order to allow optimal sampling of diisocyanates. Their sampling capability was evaluated in a controlled environment test-chamber were patches were exposed to increasing concentrations of diisocyanates.The UPLC-MS/MS method using a Unispray ionisation source, based on supercritical fluids ionisation and Coanda effect, allowed reaching very low levels of detection (LoD=1 pg/mL) for all the targeted compounds (i.e. 4,4-MDI, 2,4-MDI, 2,6-TDI, 2,4-TDI, 1,6-HDI, and IPDI). Due to the high sensitivity of the analytical method, very low levels of diisocyanates (i.e. 25 pg/patch) are detected on the custom-made dermal patches. Furthermore, the patches allowed the sampling of a broad range of concentration levels (from 5 pg/cm2 to 5 ng/cm2), which have been correlated with the air levels from the controlled environment chamber-test.We succeeded to develop a method to assess dermal exposure to diisocyanates. Field studies are now necessary to further evaluate the suitability of the custom-made patches, as well as to relate low levels of exposure and potential health outcomes.