Optical detection of volatile electron deficient analytes via fluorescence quenching is demonstrated using ca. 200 nm diameter template-synthesized polyfluorene nanofibers as nanoscale detection elements. Observed trends in analyte quenching effectiveness suggest that, in addition to energetic factors, analyte vapor pressure and polymer/analyte solubility play an important role in the emission quenching process. Individual nanofibers successfully act as luminescent reporters of volatile nitroaromatics at sub-parts per million levels. Geometric factors, relating to the nanocylindrical geometry of the fibers and to low nanofiber substrate coverage, providing a less crowded environment around fibers, appear to play a role in providing access by electron deficient quencher molecules to the excited states within the fibers, thereby facilitating the pronounced fluorescence quenching response.