(4-Fluorobenzyl)triphenylphosphonium hexachlorozirconate [Ph3PCH2C6H4F-4][ZrCl6] (I) is synthesized by the reaction of (4-fluorobenzyl)triphenylphosphonium chloride with zirconium tetrachloride in an acetonitrile solution. The structure of the compound is characterized by IR spectroscopy, H-1, C-13{H-1}, and F-19{H-1} NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction (XRD). According to the XRD data, the crystals of complex I (CIF file CCDC no. 2063132) consist of tetrahedral (4-fluorobenzyl)triphenylphosphonium cations (CPC 99.44(13)degrees-114.94(12)degrees, P-C 1.706(2)-1.935(3) angstrom) of two types and octahedral anions [ZrCl6](2-) (trans-ClZrCl angles 177.35(3)degrees-178.62(3)degrees, distances Zr-Cl 2.4308(9)-2.5350(11) angstrom). The structure of complex I is formed due to weak hydrogen bonds between the cations and anions. The IR spectrum of complex I exhibits an intense band of stretching vibrations of the F-C-Ar bond at 997 cm(-1), a band of vibrations of the P-C-Ar bonds at 1439 cm(-1), and bending and stretching C-H vibration bands at 743 and 3059, 2912 cm(-1). The doublet due to the long-range interaction on the fluorine atom (J = 8.8 Hz) is the characteristic signal in the P-31 NMR spectrum of complex I. All signals of the carbon atoms in the C-13 NMR spectrum are observed as doublets and doublet-doublets due to the direct and long-range interactions with the fluorine and phosphorus atoms.