Trivalent europium (Eu3+) complexes are attractive materials for luminescence applications if energy transfer from antenna ligands to the lanthanide ion is efficient. However, the microscopic mechanisms of the transfer remain elusive, and fundamental physical chemistry questions still require answers. We track the energy transfer processes in a luminescent complex Eu(hfa)(3)(DPPTO)(2) (hfa, hexafluoroacetylacetonate; DPPTO, 2-diphenylphosphoryltriphenylene) using time-resolved photoluminescence spectroscopy. In addition to the conventional energy transfer pathway through the T-1 state of the ligands, we discovered ultrafast energy transfer pathway directly from the singlet excited states of the ligands to the D-5(1) state of Eu3+. The short time scale of the energy transfer (3 ns, 200 ns) results in its high photoluminescence quantum yield. The discovery of the distinct energy transfer pathways from a single chromophore is important for establishing design strategies of luminescent complexes.