Enantiopure Ti(IV) complexes bearing pseudo-C3 amino triphenolate ligands have been synthesized and characterized. The complexes bearing ortho phenyl groups act as 1H NMR chiral solvating agent (CSA) for the stereochemical analysis of a series of sulfoxides. The coordination of a Lewis base coligand (sulfoxide) and the presence of aromatic rings are the key structural factors for the efficiency of the CSA.