The binding of 2-anthrylmethylpyrrole with halide anions has been investigated by means of fluorescence spectroscopy and ab-initio theoretical calculations. The synthesized compound exhibits highly selective binding properties with fluoride over chloride and bromide, through a preferred hydrogen bond interaction. The formation of this supramolecular adduct increases the electron density on the pyrrole unit which becomes an efficient intramolecular quencher of the fluorescence of the anthracene moiety via a photoinduced electron transfer process.