In the present work we give an overview of the CF2 (OF) 2 radical reactivity and report the synthesis of new perfluorovinylethers. CF2 CF OCF2OCF2CF3 and CF2 CF OCF2OCF2CF2OCF3 are prepared in a semi-continuous methodology starting from CF2 (OF) 2. These highly reactive vinylethers are characterized by the OCF2O group directly bonded to the insaturation. For this reason they are excellent candidates for the ...