In this article, the synthesis, density functional theory (DFT) structural characterization, and spectroscopic investigation of chiral and heteroleptic Tb(III) and Eu(III) complexes are presented. These molecules are characterized by two different ligands: the enantiopure N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N'-diacetic acid (H2bpcd) and a hydroxycoumarin-based ligand bearing different substituents in C(3) position (i.e., acetyl group in Coum, ethyl ester in CoumA, secondary and tertiary amides in CoumB and CoumC, respectively). The coumarin ligands exhibited different luminescence sensitization efficiency toward Tb(III) and Eu(III) ions in the related complexes of chemical formula [Ln(bpcd)(Coum)], [Ln(bpcd)(CoumA)], [Ln(bpcd)(CoumB)], [Ln(bpcd)(CoumC)]. Through theoretical calculations of intramolecular energy transfer (IET) processes (ligand-to-metal) in Eu(III) and Tb(III) complexes, along with quantum yield calculations, we provide a reasonable explanation for the observed differences in their luminescence properties. The nature of the coumarin ligand also affects the chiroptical properties of the Tb(III) complexes [i.e., circularly polarized luminescence (CPL) and electronic circular dichroism (ECD)].