A series of europium and gadolinium complexes comprising a β-diketone moiety modified with a fluorinated side-group and thiophene ring have been designed and synthesized and a comparative study of their luminescence properties has been carried out. In this study, when the methyl side group was modified by sequential addition of fluorine substituents and then the perfluorinated carbon chain was extended up to n-C8F17 by adding CF2 fragments, it transpired that the non-radiative energy processes are significantly suppressed in structurally more rigid polyfluorinated β-diketonate compounds of the series as C-H oscillators are replaced with low-energy C-F oscillators. The impact of other electron-withdrawing and electron-donating substituents on the spectroscopic and photophysical properties of the complexes in the present study has also been observed. Despite the presence of low-lying ligand-to-metal charge transfer states, the fluorinated Eu3+ complexes proved to be bright luminophores capable of delivering ca. 50% quantum yield under UV radiation. The role of fluorination and carbon chain length was examined by using experimental spectroscopic methods and the results obtained were largely in good agreement with theoretical calculations (Judd-Ofelt theory analysis, and semiempirical quantum chemistry calculations) supporting our key experimental findings.