Diquats—which are important electron transfer agents in biological and photocatalytic systems, as well as structural templates for efficient supramolecular synthesis—are noteworthy for their axial chirality and have been so far reported only in racemic form due to the rapid interconversion between the atropoisomers. We now report the first example of configurational ordering of chiral diquats through their asymmetric ion pairing with novel hexacoordinated phosphate anions TRISPHAT, HYPHAT and BINPHAT.