||Due to highly sensitive quenching responses of p-type poly(p-phenyleneethylene)s (PPEs) towards analytes such as 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (DNT), thin films of PPEs have successfully been applied in sensing explosives. This outstanding selectivity is highly influenced by the binding strength between the polymer and analytes. In the case of strongly binding nitroaromatic compounds such as DNT and TNT, the analyte diffusion into the PPE thin films was limited to approximately 4 nm, leading to reduced sensitivity in thick films. Herein, we report a preparation of nanoporous thin films of p-type PPE through non-solvent vapor induced phase separation (NVIPS). Thin films with well-defined nanopores have been obtained and the pore structure was easily controlled by varying film formation parameters as well as the chemical structure of PPEs. We expect that the introduction of nanoporosity within PPE films would lead to the enhanced diffusion rate of analytes into the film, resulting in the higher sensory response compared to conventional non-porous thin films.