Chiral phosphoric acid diesters arguably constitute the most exploited class of catalysts in asymmetric Brønsted acid catalysis. Despite being highly investigated for their acidic properties, these compounds display an amphoteric nature, which has instead been considerably overlooked. The potential of this dichotomous polarity has recently been disclosed and applied to the development of novel reaction modes in organocatalysis. In this account, we present our recent advances in this area, focusing on the establishment of heterodimeric interactions toward the nucleophilic activation of carboxylic acids, thiocarboxylic acids and ketones (via their enols) in asymmetric transformations