The synthesis, spectroscopy, and fluorescence quenching behavior of pentiptycene-derived phenyleneethynylene polymers, 1-3, are reported. The incorporation of rigid three-dimensional pentiptycene moieties into conjugated polymer backbones offers several design advantages for solid-state (thin film) fluorescent sensory materials. First, they prevent,pi-stacking of the polymer backbones and thereby maintain high fluorescence quantum yields and spectroscopic stability in thin films. Second, reduced interpolymer interactions dramatically enhance the solubility of polymers 1-3 relative to other poly(phenyleneethynylenes). Third, the cavities generated between adjacent polymers are sufficiently large to allow diffusion of small organic molecules into the films. These advantages are apparent from comparisons of the spectroscopic and fluorescence quenching behavior of 1-3 to a related planar electron-rich polymer 4. The fluorescence attenuation (quenching) of polymer films upon exposure to analytes depends on several factors, including the exergonicity of electron transfer from excited polymer to analytes, the binding strength (polymer-analyte interactions), the vapor pressure of the analyte, and the rates of diffusion of the analytes in the polymer films. Films of 1-3 are particularly selective toward nitro-aromatic compounds. The dependence of fluorescence quenching on film thickness provides an additional criterion for the differentiation of nitro-aromatic compounds from other species, such as quinones. In short, thinner films show a larger response to nitro-aromatic compounds, but show a lower response to quinones. Such differences are explained in terms of polymer-analyte interactions, which appear to be electrostatic in nature. The rapid fluorescence response (quenching) of the spin-cast films of 1-3 to nitro-containing compounds qualifies these materials as promising TNT chemosensory materials.