A simple and rapid method is described for detecting nitroaromatic explosives in air or seawater with the use of photoluminescent organosilicon compounds. The synthesis, spectroscopic characterization, and fluorescence quenching efficiency of silafluorenes are reported. Silafluorenes were synthesized from the reduction of dilithiobiphenyl with dichlorosilanes. Two silafluorenes were used for the detection of nitroaromatic compounds. Detection of nitroaromatic molecules, such as 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT), and picric acid (PA), has been explored. A linear Stern-Volmer relationship was observed for the first three analytes. Fluorescence spectra of silafluorenes obtained in either toluene solutions or thin films displayed no shift in the maximum of the emission wavelength. The photoluminescence quenching occurs by a static mechanism.