Chiral nucleophilic catalysts, 6-aryl-phenyl-dihydroimidazoquinolines (PIQs), were designed, synthesised and applied to the kinetic resolution of arylalkyl carbinols with very high selectivity (S) factors (up to 530). Density functional theory calculations indicate that multiple noncovalent interactions play a key role in chiral recognition between 6-aryl-PIQ catalysts and chiral secondary alcohol substrates.