We report the synthesis of a series of poly(Erphenylene ethynylene)s (PPEs) with high ionization potentials and associated high excited-state electron affinities. Their photophysical properties were investigated using steady-state and time-resolved fluorescence techniques. The ionization potentials of the polymer thin films were determined using ultraviolet photoelectron spectroscopy (UPS), and those with the highest ionization potentials displayed high sensitivity for the detection of electron-donating aromatic compounds. The effects of sterics, chemical structure, and electronic properties on the polymers' sensory responses were investigated by fluorescence quenching experiments in both solution and solid thin films. In addition, we report that in some cases the excited-state charge-transfer complexes (exciplexes) of the PPEs with analytes were observed. These latter effects provide promising opportunities for the formation of sensitive and selective chemical sensors.