Hybrid materials based on lanthanide ions or lanthanide doped nanostructured particles have received a lot of recent attention because organic ligands can sensitize RE ions via the “antenna effect.” With the aim of obtaining efficient emission via Eu3+ions, luminescent hybrid powders of Gd2O3:Eu3+ were decorated with thenoyltrifluoroacetone (TTA) by the sol–gel method. This article reports on the influence of the organic ligand on the luminescent properties by varying the TTA: Gd2O3:Eu3+ molar ratios: X:1 (X = 0.08, 0.16, 0.32, and 0.48). The precursors used to elaborate the TTA/Gd2O3:Eu3+ hybrid systems were gadolinium and europium nitrates, with ethanol used as a solvent. Gd2O3:Eu3+, modified nanopowders were previously synthesized by the sol–gel process and heat treated at 800 °C in the presence of Pluronic F 127; this fact was due to the observed enhanced luminescence intensity promoted by Pluronic F 127. For all of the hybrid systems, the x ray diffraction results showed a Gd2O3:Eu3+ TTA cubic structure, without structural changes. FTIR studies revealed the presence of new bands besides those related to Gd–O, which suggests that Gd2O3:Eu3+ was successfully capped by TTA. The TTA/ Gd2O3:Eu3+ hybrid systems presented a stronger luminescence intensity than those of the non hybrid systems; this effect is due to an energy transfer from the 2 thenoyltrifluoroacetone ligands to the Gd2O3:Eu3+ particles. In this study, the effect of TTA on the structural, morphological, and luminescence properties of TTA/ Gd2O3:Eu3+ hybrid systems was investigated. (a) PL emission intensities Gd2O3:Eu3+, TTA: Eu3+ (b) scheme of the TTA/Gd2O3:Eu3+ system.