Several poly(phenylene ethynylene)s with pendant hexafluoro-2-propanol (HFIP) groups have been synthesized and characterized in terms of their solution and thin-film optical properties. The incorporation of strongly hydrogen-bond-donating HFIP groups into conjugated polymers is shown to greatly enhance their fluorescence response upon exposure to the vapors of several hydrogen-bond-accepting analytes such as pyridine and 2,4-dichloropyrimidine. The enhanced sensitivity of these conjugated polymer-based chemosensors is the result of stronger analyte/polymer binding interactions and more facile photoinduced charge-transfer reactions with hydrogen-bonded analytes.