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Trichloroiodosilane can be used as selective ether-cleaving reagent; also cleaves acetals; mediates reaction of aromatic aldehydes with nitriles to yield secondary amides;aromatic aldehydes and acrylonitrile give iminoaldehydes.

It is prepared through halogen exchange by heating SiCl4 and sodium iodide in methylene chloride– acetonitrile or toluene–acetonitrile. It also has been prepared by the reaction of SiCl4 and hydrogen iodide, by heating SiHCl3 with iodine, and by heating silicon with ICl.