A sampling, modulation, and separation (SMS) unit was tested for detection of hazardous chemicals. The SMS unit, designed and developed for on-site sampling and analysis, consists of a dynamic inlet system coupled with a fast, miniaturized gas chromatograph (GC). Feasibility of the SMS unit was evaluated together with a hazardous chemical vapor generator. The performance of the SMS unit was tested with automated thermal desorption after SMS to collect samples for GC-mass spectrometry (GC-MS) measurements. Detection of sarin nerve agent was verified. Additionally, the vapor generator was connected to the SMS unit, which was hyphenated with a photoionization detector (PID), thus creating a fast GC-PID system. This system gave a positive response for degradation products of sulfur mustard, thereby indicating suitability of the SMS-PID unit for field drone applications.