A new beta-diketone, 5,6-dimethoxy-2(2,2,2-trifluoroethyl)-1-indone (5,6-DTFI), has been designed and synthesized. Two series of four 5,6-DTFI Sm3+ and Eu3+ complexes, namely, Eu(5,6-DTFI)(3)(H2O)(2) (1), Eu(5,6-DTFI)(3)(Phen) (2), Sm(5,6-DTFI)(3)(H2O)(2) (3) and Sm(5,6-DTFI)(3)(Phen) (4) (Phen = 1,10-phenanthroline), have been isolated. X-ray diffraction analysis reveals that all complexes 1-4 are of mononuclear structures. Luminescent and phosphorescent spectra of complexes 1-4 show strong characteristic emissions of the corresponding Eu3+ and Sm3+ ions. Upon complexes 1 and 2 were doped into the poly(methylmethacrylate) (PMMA) forming the films, the PMMA polymer matrix acting as a co-sensitizer for Eu3+ ion enhances the luminescent lifetimes, overall quantum yields and the thermal stability in comparison with the precursor complexes.