Ditopic helicate ligands 1 and 2 were synthesized for the formation of dinuclear Eu(III )luminescent chiral helical assemblies (Eu-2 center dot L-3) in competitive organic and protic solvent media. Spectroscopic analysis revealed formation of the 2:3 (Eu-2 center dot L-3) and 2:2 (Eu-2 center dot L-2) species in methanolic solutions. Circular dichroism and circularly polarized luminescence (CPL) spectroscopy confirmed the chiral purity of the helical systems, while scanning electron microscopy imaging demonstrated the formation of hierarchical self-assemblies with spherical morphologies.