A new terbium 2-isopropylimidazole-4,5-dicarboxylic acid complex was prepared and incorporated into titanium dioxide matrix by mild sol–gel method. Then we fabricated a terbium luminescent hybrid material, which displayed striking green emission even in pure water. It was interesting to find that this target material exhibited highly selective and fast (1 s) quenching effect to F⁻ compared with CH₃COO⁻, Cl⁻, Br⁻, I⁻. We recognized that the hydrogen bonding interactions between fluoride and ligand resulted in the recognition process. More significantly, this hybrid titania material prepared under low temperature (80 °C) could be used in photodegradation of methyl orange in aqueous environment.