Inherently chiral phosphonatocavitands with various bridging moieties at their wide rim were synthesized. Optical resolution by chiral HPLC was performed with cavitand 8 to afford enantiopure compounds (+)-8 and (−)-8. The molecular structures of hosts 8 and 12 were determined by X-ray diffraction. The host properties were investigated by ¹H and ³¹P NMR spectroscopy. The phosphonatocavitands form inclusion complexes with chiral ammonium neurotransmitters, some presenting enantioselectivity towards the right or left-handed host enantiomers.