The N(CH3)(4) salt of the CiS-IO2F32- anion was synthesized from [N(CH3)(4)][IO2F2] and excess [N(CH3)(4)][F] in CH3CN solvent. The [N(CH3)(4)12[IO2F3] salt was characterized by Raman, infrared, and F-19 solid-state MAS NMR spectroscopy. Geometry optimization and calculation of the vibrational frequencies at the DFT level of theory corroborated the experimental finding that the IO2F32- anion exists as a single isomer with a cis-dioxo and mer-trifluoro arrangement. The fluorine atom in IO2F32- that is trans to one of the oxygen atoms is weakly bound with a calculated bond length of 228.1 pm. The IO2F32- anion is only the second example of an AEO(2)F(3) species after XeO2F3-.