A new thin-film passive sampler is presented as a low resource dependent and discrete continuous monitoring solution for explosives-related vapours. Using 15 mid-high vapour pressure explosives-related compounds as probes, combinations of four thermally stable substrates and six film-based sorbents were evaluated. Meta-aramid and phenylene oxide-based materials showed the best recoveries from small voids (~70%). Analysis was performed using liquid chromatography-high resolution accurate mass spectrometry which also enabled tentative identification of new targets from the acquired data. Preliminary uptake kinetics experiments revealed plateau concentrations on the device were reached between 3–5 days. Compounds used in improvised explosive devices, such as triacetone triperoxide, were detected within 1 hour and were stably retained by the sampler for up to 7 days. Sampler performance was consistent for 22 months after manufacture. Lastly, its direct integration with currently in-service explosives screening equipment including ion mobility spectrometry and thermal desorption mass spectrometry is presented. Following exposure to several open environments and targeted interferences, sampler performance was subsequently assessed and potential interferences identified. High-security building and area monitoring for concealed explosives using such cost-effective and discrete passive samplers can add extra assurance to search routines while minimising any additional burden on personnel or everyday site operation.