In this paper, we report the synthesis and mesoporous film formation of hydrophobic rodlike poly( p-phenyleneethynylene)s (PPEs) and present porosity-dependent quenching studies using 1,3,5-trinitrotoluene (TNT) vapors. Nonsolvent vapor-induced phase separation was used to induce pore formation during film casting, and the concentration of PPEs in the casting solution was controlled carefully to prevent excimer formation. We found that the structures of the sidechains of the PPEs strongly influence the range of relative humidity at which controlled pore generation occurs, which could be rationalized from interfacial energies calculated from contact angle measurements. Porosity of the PPE films resulted in increased efficiency of fluorescence quenching toward TNT vapors, which previously required very thin films (below 5 nm) for sensing applications. The control of the porous structure as well as film thickness constitutes a promising strategy for enhancing the efficiency of chemosensors and in more general applications requiring fine-tuned polymer-gas interactions.