Chemical sensors based on fluorescent quantum dots have attracted intense interest because of their excellent optical and electronic properties compared to the routinely employed fluorescent organic dyes. This study reports a CdSe QD-polymer-based luminescent chemosensor, which is based on an array containing either green-emitting or red-emitting CdSe QDs embedded in polycaprolactone as a polymer host matrix. We evaluate the sensing capability of the nanocomposites by exposing both sensors to vapors of explosive taggants, explosive-like molecules, and some common solvents. Both nanocomposites exhibit a very fast response time of <30 s. The limit of detection of the sensors for 3-nitrotoluene, 4-nitrotoluene 2,3-dimethyl-2,3-dinitrobutane, and picric acid was found to be 0.055, 2.7, 0.7 and 916.4 ng, respectively. The sensor array constitutes a powerful tool to discriminate between explosive taggants (3-nitrotoluene, 4-nitrotoluene, and 2,3-dimethyl-2,3-dinitrobutane) and shows specific molecular recognition toward picric acid. This type of miniaturized luminescent QD-based nanocomposites might form the basis of a sensing platform technology to perform effective chemical detection and identification of explosive taggants preblast and postblast.