The oxidation of 4:4′-bi(2,6-diphenyl-1-selenopyranylidene)2 with iodine leads to a radical cation iodide salt of stoichiometry ≊ 1:2. The structure was established by X-ray crystallography and compared to that of the corresponding sulfur compound. In addition to the Bragg reflections, diffuse streak on rotation photographs indicate disordered lattices incommensurate alongcwith a repeat ofc′ ' 10.95 Å. The Raman spectra of this radical cation iodide salt shows two kinds of iodide speciesI−3andI−5with a relative concentration of 3.4, corresponding to a stoichiometry of 2-I2.03. TheIRand Raman spectra [1000–1700 cm−1range of some 4:4′-bi(chalcogenopyranylidenes) are described and compared with the 2-I2.03spectra.