A sensing system for explosives is provided. The sensor is based on a layered structure of approximately a monolayer of a fluorophore deposited onto a few nm of a transparent polymer, supported by a substrate. The fluorophores can be xanthene laser dyes, which have high quantum yields, and the polymers can be commodity materials polymethylmethacrylate and polyvinylidene difluoride. The different fluorophore/polymer combinations give different emission responses to analytes, including both signal quenching and enhancement. The pattern of responses can be used to identify the analyte. The common explosives TNT, PETN, RDX, HMX, and TATP as gas phase species can all be uniquely identified at room temperature using only the natural vapor pressure of the explosive to deliver sample to the sensor.