Methoxy-(2,2,2-trifluoroethoxy)carbene radical cations, CH3O-C-OCH2CF3•+, 1•+, are cleanly generated by the dissociative electron ionization (EI) of 2-methoxy-5,5-dimethyl-2-(2,2,2-trifluoroethoxy)-Δ3-1,3,4-oxadiazoline I. Neutralization–reionization (NR) mass spectrometry of the neutral carbene 1, generated by one-electron reduction of 1•+, shows no recovery ion signal and thus 1 is not a viable species within the μs time scale of the experiment. Very low vapour pressure (VLVP) pyrolysis – mass spectrometry of I in conjunction with (multiple) collision experiments shows that 1 completely isomerizes, via a 1,2-trifluoroethyl shift, into methyl 3,3,3-trifluoropropionate, CF3CH2C(=O)OCH3, 1a. This technique was also used to study the related dialkoxycarbenes C2H5O-C-OCH2CF3, 2, CH3O-C-OC2H5, 3, and CH3O-C-OCH(CH3)2, 4, generated from the corresponding 2,2-dialkoxy-5,5-dimethyl-Δ3-1,3,4-oxadiazolines. The pyrolytically generated carbene 2 behaves analogously to 1 and completely isomerizes to ethyl 3,3,3-trifluoropropionate, 2a. The neutral carbenes 3 and 4 undergo only a partial isomerization via 1,2-alkyl shifts in which the ethyl and isopropyl groups show a slightly greater migratory aptitude, respectively, than the methyl group. The differences in migratory aptitude are explained in terms of a transition state model similar to that of a 1,2-H shift in carbenes, with development of negative charge in the migrating group. The greater migratory aptitude of CF3CH2, as compared to CH3 and CH3CH2, is attributed to the stabilization of negative charge in the transition state by strongly electron-withdrawing β-fluorines whereas the differences in migratory aptitude between the alkyl groups in 3 and 4 are largely due to the greater polarizability of isopropyl and ethyl groups, as compared to the methyl group. Key words: dialkoxycarbenes, pyrolysis, tandem mass spectrometry.