Three new tetranuclear europium(III) alternating circular helicates, (2-(RRRR)-R-Ph/2-(SSSS)-S-Ph) [(R)- or (S)-Ph-Py-box](4)Eu-4(III)(BPP)(6), (2-(RRRR)-R-iPr/2-(SSSS)-S-iPr) [(R)- or (S)-Pr-i-Py-box](4)Eu-4(III)(BPP)(6), and (3- (RRRR)-R-Ph/3-(SSSS)-S-Ph) [(R)- or (S)-Ph-Pybox](4)Eu-4(III)(BHP)(6), are presented with their structural and chiroptical characterization (BPP and BHP = bis-beta-diketonates; Pybox = chiral bis(oxazolinyl) pyridine ligand). X-ray crystallographic analysis revealed that different extents of interligand-contacting interactions between bis-beta-diketonates and Pybox ligands produce different bis-beta-diketonates arrangements around four Eu-III ions and, thus, their specific symmetry in the final tetranuclear complexes. 2-(RRRR)-R-Ph/2-(SSSS)-S-Ph and 3-(RRRR)-R-Ph/3-(SSSS)-S-Ph are recognized as D2-symmetry, while 2-(RRRR)-R-iPr/2-(SSSS)-S-iPr self-assemblies possess pseudo C-2h-symmetry. Due to different molecular symmetry, 2-(RRRR)-R-Ph/2-(SSSS)-S-Ph and 2-(RRRR)-R-iPr/2-(SSSS)-S-iPr crystals display different ligands orientation in their Eu-III coordination spheres. The presence of pseudo sigma(h)-mirror symmetry in 2-(RRRR)-R-iPr/2-(SSSS)-S-iPr promotes a pair of distinguishable Eu-III geometries. All the chiral self-assemblies exhibit almost identical photoluminescence emission spectra patterns of f-f transitions in the Eu-III core. The Eu-III self-assemblies exhibit intense CPL with different observed vertical bar g(lum)vertical bar values (2-(RRRR)-R-Ph/2-(SSSS)-S-Ph similar to vertical bar 0.31 vertical bar, 2-(RRRR)-R-iPr/2-(SSSS)-S-iPr similar to vertical bar 0.08 vertical bar, 3-(RRRR)-R-Ph/3-(SSSS)-S-Ph similar to vertical bar 0.31 vertical bar in chloroform).