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In the crystal structure of the title compound, NH4+·PF6−·C12H24O6, the cation is situated in the 18-crown-6 ring, forming a supramolecular rotator-stator-like structure held by N—H...O hydrogen bonds. The six O atoms of the crown ether lie approximately in a plane [mean deviation 0.2129 (3) Å]; the N atom is displaced by 0.864 (3)Å from the centroid of the 18-crown-6 ring. The slightly distorted tetrahedral cations further interact with the slightly distorted octahedral anions via intermolecular N—H...F hydrogen bonds.