In this Letter, a time-resolved 120 × 128 pixel single-photon avalanche diode (SPAD) sensor is used in conjunction with an array of organic semiconductor films as a means of detecting the presence of explosive vapors. Using the spatial and temporal resolution of the sensor, both fluorescence intensity and fluorescence lifetime can be monitored on a pixel-by-pixel basis for each of the polymer films arranged in a 2 × 2 grid. This represents a significant improvement on similar systems demonstrated in the past, which either offer spatial resolution without the temporal resolution required to monitor lifetime or offer only a single bulk measurement of lifetime and intensity without the spatial resolution. The potential of the sensing system is demonstrated using vapors of DNT, and differing responses for each of the four polymer films is observed. This system has clear applications as the basis of a portable chemical fingerprinting tool with applications in humanitarian demining and security.