The luminescence and circularly polarized luminescence (CPL) spectra of MI[Eu((+)-hfbc)4] show a similar behavior to the exciton CD in the intraligand π–π* transitions when the alkali metal ions and solvents are manipulated. There is a difference in susceptibility in solvation toward the alkali metal ions but not toward the Eu(III) ion, as in the case of axially symmetric DOTA-type compounds. The remarkable CPL in the 4f–4f transitions provide much more information on the stereospecific formation of chiral Eu(III) complexes, since CPL spectroscopy is limited to luminescent species and reflects selectively toward helicity of the local structural environment around the lanthanide(III). While in comparison, exciton CD reveals the chiral structural information from the helical arrangement of the four bladed chelates. Of special importance, the observation of the highest CPL activities measured to date for lanthanide(III)-containing compounds (i.e., Eu and Sm) in solution supports the theory that the chirality of lanthanide(III) in the excited state corresponds to that in the ground state, which was derived from the exciton CD.