The crystal structure of the novel iodine compound Cl2IOI(O)F2 is described. Cl2IOI(O)F2 contains iodine in two different oxidation states (III) and (V) and can formally be described as ICl2+IF2O2−, linked by an unsymmetrical, nonlinear I−O−I bridge, with I−O bond lengths of 1.84(1) Å and 2.32(1) Å, and a bond angle of 122.5(5)°. It was accidentally obtained by the uncontrolled reaction between CF3I, CF3OCl, CF2O, and Cl2 at −70 °C over a period of about six months and finally two days at room temperature. Cl2IOI(O)F2 crystallises in the monoclinic space group P21/c with four formula units per unit cell with the dimensions a = 12.910(1), b = 6.987(1), c = 7.550(1) Å, and β = 94.890(1)°. The molecule was additionally characterised by its Raman and IR spectra.