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In the title molecular salt, C22H22O2P+·PF6−, the side chain of the cation adopts an anti–gauche conformation [P—C—C—C and C—C—C—C torsion angles = −179.11 (10) and −77.18 (16)°, respectively]. In the crystal, the cations are linked into carboxylic acid inversion dimers by pairs of O—HO hydrogen bonds. Weak C—HF and C—H(F,F) hydrogen bonds connect the components into a three-dimensional network, but there are no aromatic π–π stacking interactions.