[RE(TMA)] anhydrous complexes (RE3+: Y, Gd and Lu) present high red emission intensity with a quantum efficiency (~45%) for the [Y(TMA):Eu3+] complexes, due to the absence of non-radioactive decay pathways mediated by water molecules. The complexes were prepared in mild conditions. All the compounds are crystalline and thermostable up to 460°C. Phosphorescence data of the complexes with Y, Gd and Lu show that the T1 state of the TMA3− anion has energy higher than the 5D0 emitting level of the Eu3+ ion, indicating that the ligand can act as an intramolecular energy sensitizer. The photoluminescence properties of the doped materials were studied based on the excitation and emission spectra and luminescence decay curves. The experimental intensity parameters (Ω λ), lifetimes (τ), radiative (A rad) and non-radiative (A nrad) decay rates were determined and discussed.