Chemical reactions and processes often involve chiral, yet racemic, cationic reagents, intermediates, or products. To afford instead nonracemic or enantiopure compounds, an asymmetric ion pairing of the cations with enantiopure anions can be considered - the counter ions behaving as asymmetric auxiliaries, ligands, or reagents. Detailed herein is a short review of our approach toward gaining reliable and predictable control over stereoselective ion pairing phenomena through the synthesis and use of novel configurationally stable hexacoordinated phosphate anions.