Creating optically pure metal assemblies is a hot research topic in the realms of chiral supramolecules. Here, three new triple-stranded europium(III) helicates Eu₂L₃(L′)₂ [L = 4,4′-bis(4,4,4-trifluoro-1,3-dioxobutyl)diphenyl sulphide; L′ = 1,10-phenanthroline (Phen) or R/S-2,2′-bis(diphenylphosphinyl)-1,1′-binaphthyl (R/S-BINAPO)] were synthesized in order to investigate the effects of ancillary ligands on controlling the stereoselective self-assembly of lanthanide helicates. X-ray single crystal structure analysis showed that Eu₂L₃(Phen)₂ crystalized in an achiral space group P with the equivalent amount of P and M helicates in one single cell. The isolated Eu₂L₃(S-BINAPO)₂ and Eu₂L₃(R-BINAPO)₂ were verified to be enantiopure by ¹H, ¹⁹F, ³¹P NMR and DOSY NMR analyses. Additionally, the mirror-image CD spectra also demonstrated the successful syntheses of the enantiomers and the presence of an effective chirality transformation from BINAPO to achiral L. Furthermore, the perfect mirror-image circularly polarized luminescence (CPL) spectra of Eu₂L₃(S-BINAPO)₂ and Eu₂L₃(R-BINAPO)₂ indicated the existence of the excited state chirality of the Eu³⁺ center associated with |g_lum| values reaching 0.112. In addition, the photophysical properties of three helicates were also discussed.