ABSTRACT: The excitation energy transfer (EET) pathways in the sensitization luminescence of EuIII and the excitation energy migration between the different ligands in [Eu(fod)3dpbt] [where fod=6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione and dpbt=2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine], exhibiting well-separated fluorescence excitation and phosphorescence bands of the different ligands, were investigated by using time-resolved luminescence spectroscopy for the first time. The data clearly revealed that upon the excitation of dpbt, the sensitization luminescence of EuIII in [Eu(fod)3dpbt] was dominated by the singlet EET pathway, whereas the triplet EET pathway involving T1(dpbt) was inefficient. The energy migration from T1(dpbt) to T1(fod) in [Eu(fod)3dpbt] was not observed. Moreover, upon the excitation of fod, a singlet EET pathway for the sensitization of EuIII luminescence, including the energy migration from S1(fod) to S1(dpbt) was revealed, in addition to the triplet EET pathway involving T1(fod). Under the excitation of dpbt at 410?nm, [Eu(fod)3dpbt] exhibited an absolute quantum yield for EuIII luminescence of 0.59 at 298?K. This work provides a solid and elegant example for the concept that singlet EET pathway could dominate the sensitization luminescence of EuIII in some complexes.