The photoluminescence and Raman spectra of the tris(dibenzoylmethane) europium(III) dihydrate (Eu(DBM)3•2H2O) are investigated at high pressures with a diamond anvil cell. For pressures lower than 3 GPa, the luminescent intensities of the Eu3+ ion 5D0→7FJ (J=0, 1, 2, 3, 4) characteristic peaks increase with the pressure. However, above 3 GPa the intensities decrease. The phenomena indicate that there is energy transition between the Eu3+ ion and the DBM ligand. With the increasing pressure, the intensity for the vibration bands becomes more obvious compared with that of the Eu3+ ion characteristic peaks, as the result of the crystal distortion at high pressures. The Raman bands at low wavenumbers have not shown significant changes with pressure, which manifests that the Eu3+ ion site symmetries are not varied but that the crystal is distorted at high pressures.