Given that compounds incorporating lanthanide metals are fascinating due to their peculiar optical and paramagnetic properties; this work was focused on designing new unsymmetrical and symmetrical tripodal ligands and studying their coordination properties with Ln(III) in view of potential applications (e.g. sensing and relaxivity agents). The resulting complexes with lanthanides have been examined with different methods (X-ray, NMR, ESMS, spectrophotometry) to elucidate their structure, stability, and photophysical properties in the solid state and in solution. Different types of complexes were obtained, going from unsaturated dinuclear helicates to more sophisticated edifices such as tridimensional pentanuclear helicates and self-assembled tetrahedral cages. Moreover, the impact of the ligand design on the structure and properties of the lanthanide complexes formed was discussed.