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N, N′-dicyclohexylimidazolium hexafluorophosphate was prepared and its structure was determined by X-ray diffraction. The compound crystallizes in the orthorhombic space group Pbca, with the cell dimensions of a = 14.620(3) Å, b = 15.097(3) Å, c = 16.128(3) Å, V = 3559.4(12) Å3, and Dcalc. = 1.412 mg/m3 for Z = 8. The structure was solved by direct methods and refined to R value of 0.041. In the solid state, PF6− anion and imidazolium cation form strong hydrogen bonds, which fix the relative orientation between cations and anions.