A series of functionally terminated poly(perfluoroalkylene oxides), a new class of curable, liquid, fluorinated polymers, has been prepared by the photopolymerization of perfluorooxydipropionyl fluoride, O(CF2CF2COF)2, and related perfluoroacyl fluoride monomers. Polymerization proceeds by ultraviolet-induced scission of CF2COF groups and coupling of the CF2—radicals thus formed. Polymer molecular weight and functionality increase with photolysis time. The acid fluoride-terminated polymers (Mn 1000–5000, functionality 2–5) are liquids possessing low Tg(about −60°C) and excellent, thermal stability. Other functional end groups (e.g., COOH, COOR, CH2OH, etc.) have been prepared using standard reactions.