A novel kind of luminescent ternary organic–inorganic mesoporous hybrid Eu(TTASi-SBA-15)₃phen (phen = 1,10-phenanthroline) has been assembled by the Eu³⁺ complex covalently attached to the TTA directly Functionalized ordered mesoporous SBA-15, which is characterized to have high surface area, uniformity in the mesostructure and crystallinity. The efficient intramolecular energy transfer in mesoporous material Eu(TTASi-SBA-15)₃phen mainly occurs between the modified ligand TTASi and the central Eu³⁺ ion. Furthermore, compared with the binary mesoporous material Eu(TTASi-SBA-15)₃, the ternary mesoporous material Eu(TTASi-SBA-15)₃phen exhibits the characteristic emission of the Eu³⁺ ion with a higher luminescence quantum efficiency intensity and a longer lifetime, suggesting that the introduction of ligand phen into the mesoporous matrix is of benefit for the sentisization of Eu³⁺luminescence, by replacing H₂O groups that can quench the luminescence of Eu³⁺ ions.