We report time-resolved X-ray absorption near edge structure (TR-XANES) measurements at the Eu L3 edge upon photoexcitation of several Eu(III)-based luminescent lanthanide complexes. We find an unambiguous signature of the 4f intrashell excitation that occurs upon energy transfer from the photoactive organic antennas to the lanthanide species. Phenomenologically, this observation provides the basis for direct investigation of a crucial step in the energy transfer pathways that lead to sensitized luminescence in lanthanide-based dyes. Interestingly, the details of the TR-XANES feature suggest that the degree of 4f-5d hybridization may itself vary depending on the excited state of the Eu(III) ion.