MF6- (M = As or Sb) salts of a simple derivative of the trithietanylium PhCSSS+, 1, were synthesized for the first time by the reaction of PhCS3Cl and AgMF6 in liquid SO2. 1SbF(6) was characterized by IR, FT-Raman, and NMR spectroscopy, elemental analysis, and a preliminary X-ray crystal structure. 1AsF(6) was characterized by H-1 NMR and FT-Raman spectroscopy. The calculated (MPW1PW91/3-21G* or 6-31G*) geometries, H-1 and C-13 chemical shifts (MPW1PW91/6-311G(2DF)//MPW1PW91/3-21G*), and vibrational frequencies and intensities (MPW1PW91/6-31G*) were in satisfactory agreement with the observed values. The calculated pi type molecular orbitals of HCSSS+ (MPW1PW91/6-311+G*) and 1 (MPW1PW91/3-21G*) imply that the 6 pi-CSSS+ ring has some aromatic character. 1SbF(6) undergoes a metathesis reaction with NBu4Cl in liquid SO2 to give PhCS3Cl, which was characterized by vibrational spectroscopy and mass spectrometry. The evidence indicates that PhCS3Cl has the ionic formulation PhCSSS+Cl-, with significant cation-anion interactions in the solid state. ArCSSS+SbF6- (Ar = 1-naphthyl), 14SbF(6), was prepared from ArCS3Cl and AgSbF6, suggesting that the synthesis of MF6- (M = As or Sb) salts of RCSSS+ is potentially general for aryl derivatives. The structure of 14SbF(6) was established by H-1 and C-11 NMR, IR, and FT-Raman spectroscopy, and theoretical calculations gave values in agreement with the experimental data.