2,3,8,9-Tetramethoxydibenzo[c,e][1,2]dithiin (“dithiobiphenyl” = “DTB”) forms a host lattice for iodine. Electron transfer from DTB to iodine leads to the formation of an organic semiconductor with the approximate formula of DTB·I1.16. This host−guest complex can be prepared either by cocrystallization of both compounds from solution or by treating solid DTB with gaseous iodine. Upon heating, iodine is released again. Both intercalation and deintercalation were studied with physicochemical methods, among them thermal analysis, electron paramagnetic resonance (EPR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and thermomicroscopy.