Trifluoromethylketene has been detected by trapping reactions, but has not been isolated. In the absence of a trapping agent, reactions designed to give the ketene gave its isomer, perfluoroacryloyl fluoride. Convenient syntheses are described for saturated precursors to perfluoroacryloyl fluoride, methyl perfluoroacrylate and methyl perfluoromethacrylate, and conditions are given for the dehydrofluorination of these precursors to the acrylates. Some chemistry of perfluoromethacryloyl fluoride [available from bis(trifluoromethyl)ketene through equilibration], perfluoroacryloyl fluoride and the related methyl esters are reported, particularly Michael additions, 1,2 cyclo-additions and free-radical reactions.