[en] The luminescence behavior of the europium (Eu) complexes with hexafluoracetylacetonate (HFA:Eu³⁺ complexes) in the ORMOSIL matrices has been investigated. The steady-state excitation and emission spectra of the 1 mol.% EuCl₃ and the 3 mol.% hexafluoracetylacetonate (HFA) co-doped gel were similar to that of the HFA:Eu³⁺ complexes powders which were synthesized in ethanol solution, which indicated that the HFA:Eu³⁺ complexes have been synthesized in the 1 mol.% EuCl₃ and the 3 mol.% HFA co-doped gel. The time-resolved spectra of the 1 mol.% EuCl₃ and 3 mol.% HFA co-doped gel exhibited the ligand-to-metal energy transfer process, which also confirmed the synthesis of the HFA:Eu³⁺ complexes in the 1 mol.% EuCl₃ and 3 mol.% HFA co-doped gel. The decay curves of the luminescence ⁵D₀ state obtained by monitoring the ⁵D₀→⁷F₂ emission line for the HFA:Eu³⁺ complexes powders and for the 1 mol.% EuCl₃ and 3 mol.% HFA co-doped gel could both be fitted to a single-exponential fitting function. The temperature of heat treatment has significant influence on the luminescence behavior of the 1 mol.% EuCl₃ and 3 mol.% HFA co-doped gel. The luminescence intensities of the 1 mol.% EuCl₃ and 3 mol.% HFA co-doped gel reached a maximum at approximately 110 deg. C and decreased gradually with increasing temperature. However, the ⁵D₀ excited-state lifetimes of the Eu³⁺ ions in the 1 mol.% EuCl₃ and 3 mol.% HFA co-doped gels increased gradually with increasing temperature