As a result of an extensive delocalization of charge and a unique covalent structure, the cation has, in CH 3 OCH 2 ' e โ ect, the character of an ambident electrophile. This cation can, on the one hand, be considered to be a classical electrophile. On the other hand, it may be considered to be a facile methyl cation donor. The former character predominates when this cation reacts with alcohols, as is shown in this work. In both the chemical ionization (CI) source of a conventional mass spectrometer and also via low-pressure bimolecular reactions in a Fourier transform ion cyclotron resonance (ICR) cell, the dominant reaction between alkoxymethyl cations and alcohols is the very exothermic formation of a CรO bond to give a covalent adduct having the structure of a protonated dialkoxymethane. A 1,3-hydrogen transfer is observed for the covalent adducts. In the case of those generated in the ICR cell this process is a slow unimolecular reaction. However, the rapid 1,3-hydrogen transfer observed in the CI source is a bimolecular reaction catalysed by a second molecule of alcohol. This is a new example of catalysed isomerization in the gas phase. In competition with the 1,3-hydrogen transfer, the covalent adducts may either undergo simple bond cleavage or may isomerize to proton-bound dimer adducts of ether and aldehyde (or ketone) via a hydride transfer mechanism. This mechanism either may involve an electrostatic complex intermediate or may be an asynchronous concerted process. Since the proton affinities of the ethers involved in these proton-bound dimer intermediates are greater than those of the aldehydes derived from primary alcohols, such dimers dissociate to yield protonated ether and aldehyde. Conversely, those dimers resulting from secondary alcohols involve ketones whose proton affinities are greater than those of the partner ethers and these dimers dissociate to yield protonated ketone and ether. In summary, the reactions of with alcohols occur via several successive and speciรc CH 3 OCH 2 ' steps.