2,3,5-Triphenyltetrazolium hexachlorophosphate, [C 19 in dry acetonitrile, and their crystal structures were determined by single-crystal X-ray diffraction analysis. In the title compounds, the [TPT] + cations show a face-to-face stacked orientation between the phenyl rings of neighboring molecules, which is caused by intermolecular π ···π interactions. The crystal structure of compound 1 consists of layers of 2,3,5-triphenyltetrazolium cations and hexachlorophosphate anions. In compound 2 the tetrahedral [PO 2 Cl 2 ] − anions exhibit approximate C 2v symmetry with P-O bond lengths from 1.454 to 1.463Å and P-Cl bond lengths from 2.038 to 2.050Å. The Raman spectrum of compound 1 was recorded, and the assignment of the [PCl 6 ] − Raman modes is proposed.