The fluorescent spectra in combination with gas response behavior of acrylic polymers doped with dibenzoyl(methanato)boron difluoride (DBMBF2) were studied by fluorescence spectroscopy and time-resolved fluorescence lifetime. The role of acrylic matrix polarity upon the fluorescence spectra and fluorescence lifetime was analyzed. Changes in emission of the dye doped polymers under exposure to toluene, n-hexane and ethanol were monitored. The fluorescence lifetimes were measured for the singlet excited state as well as the exciplex formed between DBMBF2 and toluene. A reduction of the transition energy to the first singlet-excited state in the four polymers was observed, compared to solution. Reversible exciplex formation, viz. a red shifted fluorescence emission was perceived when exposing the polymers to toluene, while for hexane and ethanol only reversible reduction of the fluorescence occurred. Longer singlet and shorter exciplex lifetimes were observed for non-polar matrixes. The latter mechanism is explained in function of the lower charge transfer character of the exciplex in non-polar matrixes. Additionally, the quantum yield of the dye in the polymer matrix increased almost seventh-fold compared to values for solution.