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The thermal transformations of tetrafluoroethylene under flow conditions at atmospheric pressure and 600–710°C in the presence of cyclopentadiene and hydrogen chloride as carbene acceptors lead to the formation of phenyltrifluoromethane in 3.6% yield in the former case and 1,1,1,2-tetrafluorochloroethane in 9.1% yield in the latter case in addition to other products. These results indicate the possibility of an olefin-carbene isomerization of tetrafluoroethylene to trifluoromethylfluorocarbene under these conditions. Hence, the formation of hexafluoropropylene in the thermolysis of tetrafluoroethylene may be the result of the recombination of difluorocarbene with trifluoromethylfluorocarbene.