The “donor-induced” generation of nitrosonium cation in acidified solutions of alkyl nitrites in dichloromethane is demonstrated spectroscopically. Electron-rich organic molecules, including polymethylbenzenes and thioethers, affect the donor-induced release of nitrosonium as the corresponding electron donor–acceptor complex [donor, NO⁺]. These complexes are spectrally identified using a combination of UV–vis and IR spectroscopy. The almost quantitative formation of the [donor, NO⁺] EDA complex with hexamethylbenzene and butyl sulfide as donors is verified with UV–vis spectroscopy.