In this paper, the participation of the ligand’s first triplet state in intramolecular energy transfer in europium and terbium Ruhemann’s Purple (RP) complexes is discussed. RP is the reaction product of ninhydrin and ninhydrin analogues with amino acids. A dual excitation experiment using an argon ion laser and a dye laser was conducted. This experiment does not support the participation of the ligand’s first triplet state in intramolecular energy transfer in Eu-RP and Tb-RP complexes. The mechanism of intramolecular energy transfer in these complexes is also addressed. It seems that it is quite different from those known in the literature.