The on-site and high-throughput screening of explosives has become increasingly significant in counter-terrorism and national security. We propose a simple and low-cost method for the screening of several explosives assisted by molecularly imprinted colloidal arrays within the 24-well plate. The infiltration and incorporation of various explosives in the interstitials of imprinted colloidal photonic crystals (CPC) result in red-shift and amplitude reduction of optical stop bands of the CPC. A certain linear relationship between the concentration of explosives and the Bragg’s diffraction shifts has been observed for a variety of explosives involving 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20, LOD 0.085 mM), hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX, LOD 0.102 mM), 2,4,6-trinitrotoluene(TNT, LOD 0.286 mM), 2,4-dinitrotoluene(2,4-DNT, LOD 0.089 mM), 2,6-dinitrotoluene(2, 6-DNT, LOD 0.238 mM), and 1,3,5-trinitrobenzene (TNB, LOD 0.184 mM). Significantly, pattern recognition and Principal Component Analysis (PCA) were utilized to discriminate the different explosives. The proposed method was successfully applied to the high-throughput screening of synthetic explosive solutions.