We report the preparation and X-ray crystallographic characterization of the first crystalline homoatomic polymer chain, which is part of a semiconducting pyrroloperylene-iodine complex. The crystal structure contains infinite polyiodide I-infinity(delta-). Interestingly, the structure of iodine within the insoluble, blue starch-iodine complex has long remained elusive, but has been speculated as having infinite chains of iodine. Close similarities in the low-wavenumber Raman spectra of the title compound and starch-iodine point to such infinite polyiodide chains in the latter as well.