Hydrogen triiodide adducts were prepared from N,N-dimethylacetamide, N-alkylpyrrolidone derivatives, and polyvinylpyrrolidone, and their structures were investigated by IR spectra and X-ray structure analyses and compared with the structure of povidone-iodine USP. The results suggest that the iodine in povidone-iodine USP is complexed by the polymer such that a proton is fixed via a short hydrogen bond between two carbonyl groups of two pyrrolidone rings and that a triiodide anion is bound ionically to this cation.