Inorganic nitrile halides have been studied theoretically by quantum-chemical approach and experimentally in the reactions of halogenation, nitration and nitro halogenation of aromatic compounds and alkynes. The generation of nitrile halides was eventually proved can be can be carried out using the iodine system (alkali metal halides) in the presence of alkali metal nitrates in an acetic acid medium. It has been found that the reaction can give the products of iodination, nitration, nitro halogenation, as well as products of cyclization, and oxidation depending on the nature of the halogen. To predict the products of reaction theoretical quantum-chemical calculations for intermediate particles - nitrile halides using the standard Gaussian-03 software package were carried out. The possibility of NO₂Hal formation was approved from quantum calculations. Furthermore the geometry of NO₂Hal particles and mechanism of their homo- or heterolytic decay were represented.