The formation of quasimolecular ions by alkali ion attachment in laser desorption mass spec-trometry has been investigated by using a CW CO2 laser. For molecules such as sucrose the desorption of preformed ions could be excluded. Evidence is presented for the ionization by alkali ion attachment in the gas phase. Quasimolecular ions of organic salts were found to result from cationization reactions in the gas phase and from surface reactions. Very fast cation exchange reactions have been discovered for salts and acids impinging on alkali ion emitting surfaces.