Ionized perfluoromethylvinyl ether, CF2=CFOCF3, dissociates chiefly to generate perfluoroketene ions. These were shown to produce the stable neutral perfluoroketene following electron transfer from xenon in a neutralization-reionization mass spectrometry (NRMS) experiment. The perfluoroketene molecules were metastable in the microsecond time frame with respect to their dissociation CF2=C=O --> CF2 + C=O.