The efficient syntheses of calix[6]azacryptands decorated with anion-binding groups on the narrow rim have been achieved from an 1,3,5-tris-protected calix[6]hexa-amine. These heteroditopic receptors can bind ammonium ions or organic ion pair salts with a positive cooperativity. In regard to their functionalization at the 1,3,5-phenolic positions, these compounds constitute the first examples of a second generation of C3 v symmetrical calix[6]azacryptands.