New conjugated spirosilabifluorene networks have been synthesized and characterized. They exhibit high surface areas, negligible solubility, broad chemical stability, and bright fluorescence. The materials have been analyzed as potential sensors for nitroaromatic compounds. The fluorescence of the condensed networks is quenched in the presence of picric acid (1-hydroxy-2,4,6-trinitrobenzene), nitrobenzene, and other nitroaromatics. Stern-Volmer quenching studies indicate the quenching can be modeled accurately with adsorption isotherm models incorporating a surface binding affinity heterogeneity. Results show a significant sensitivity toward nitroaromatic compounds comparable to known literature, as well as an improvement in picric acid sensitivity.