Lanthanide-based coordination compounds of molecular formula [Ln(keto)3(H2O)], where Ln=Gd, Eu and keto=ketoprofen, were synthesized and their photoluminescence features were detailed in the 12-300K interval. The emission spectra of [Eu(keto)3(H2O)] reveal a strong dependence with the temperature, well-illustrated by an unusual large blue-shift (~17cm-1) of the 5D0→7F0 transition as the temperature is raised. The arithmetic difference between the absorption spectrum of [Eu(keto)3(H2O)] with that of [Gd(keto)3(H2O)] pointed out the presence of a ligand-to-metal charge transfer (LMCT) band (320-370nm). From the [Gd(keto)3(H2O)] phosphorescence the energy of the keto-related triplet states was determined showing a large overlap with the intra-4f6 levels and a strong electron-phonon coupling. The high-resonance between the LMCT and triplet states and the Eu3+ levels leads to a strong dependence of the 5D0 lifetime value, typical of the presence of operative energy transfer processes.