AbstractThe interest for lanthanide circularly polarized luminescence (CPL) has been quickly growing for 10 years. However, very few of these studies have involved correlation between the dissymmetry factor (g_lum) and the chemical modifications in a series of chiral ligands. Four polymeric compounds of Eu(III) were prepared by using a series of binaphtyl derivatives for which the size of the π system as well as the number of stereogenic elements (i.e., the binaphtyl moiety) are modulated. The resulting {[Eu(hfac)₃((S)/(R)‐L^x)]}_n (x = 1 and 3) and {[Eu(hfac)₃((S,S,S)/(R,R,R)‐L^x)]}_n (x = 2 and 4) have been characterized by powder X‐ray diffraction by comparison with the X‐ray structures on single crystal of the Dy(III) analogs. In solution, the structure of the complexes is deeply modified and becomes monomeric. The nature of the ligand induces change in the shape of the CPL spectra in CH₂Cl₂ solution. Furthermore, a large |g_lum| = 0.12 of the magnetic‐dipole transition for the [Eu(hfac)₃((S,S,S)/(R,R,R)‐L²)] complex involving the ligand with three stereogenic elements and an extended 𝜋 system has been measured. This report also shows CPL measurements in solid state for the series of {[Eu(hfac)₃((S)/(R)‐L^x)]}_n (x = 1 and 3) and {[Eu(hfac)₃((S,S,S)/(R,R,R)‐L^x)]}_n (x = 2 and 4) polymers.