In this context, our group conducted a comprehensive theoretical investigation aimed at elucidating the preferred binding mode and its impact on enantioselectivity. Contrary to the conventional notion of a "strict ion pair" in bifunctional catalysis, our study revealed that a definitive binding mode through a HB is energetically more favourable. This highly stabilising and directional interaction was found to exert a profound influence on the control of enantioselectivity in reactions. Intriguingly, our computational analysis did not provide conclusive evidence supporting the sole existence of a discernible strict ion-pair interaction, underscoring the significance of hydrogen bonding in these systems. Consequently, these findings prompt the need for an updated definition of ion pairing within the field of phase-transfer catalysis.