This work reports on the structural and photophysical characterization of D 4 -symmetrical octanuclear circular Ln III helicates, [(R)-or (S)-i Pr-Pybox] 8 (Ln III ) 8 (THP) 8 (where Ln = Eu and Tb, THP = trianionic tris-β-diketonate, and i Pr-Pybox = chiral bis(4-isopropyl-2-oxazolinyl)pyridine). X-ray crystallographic analysis revealed that the octanuclear circular helicate possesses square antiprism architecture and consists of four [(R)or (S)-i Pr-Pybox] 2 Ln III 2 (THP) 2 asymmetric units arranged in a closed ring form. Ligand-to-ligand interactions between the THP and the i Pr-Pybox ligands have successfully directed formation of enantiopure, homoconfigurational (Δ,Δ,Δ,Δ,Δ,Δ,Δ,Δ)-R and (Λ,Λ,Λ,Λ,Λ,Λ,Λ,Λ)-S isomers. All of the nonacoordinated Ln III ions are identical and exhibit a distorted capped square antiprism (CSAP) geometry. Upon excitation of the ligand absorption band (λ = 360 nm), the circular helicates display characteristic Eu III (red, 5 D 0 → 7 F J , J = 0−4) or Tb III (green, 5 D 4 → 7 F J , J = 6−3) core f−f luminescence. The overall emission quantum yields of the circular Eu III and Tb III helicates are 0.145 and 0.0013, respectively, in chloroform. The Eu III and Tb III complexes exhibit remarkable circularly polarized luminescence (CPL) activity at their magnetic dipole transition with observed luminescence dissymmetry factors |g lum | of 1.25 ( 5 D 0 → 7 F 1 , λ = 592 nm) and 0.25 ( 5 D 4 → 7 F 5, λ = 541 nm), respectively. Exceptional |g lum | values of the circular Eu III helicates highlight the visible intensity difference between left and right circularly polarized emissions of R and S isomers in chloroform and PMMA thin film.