2-Perfluoro(alkyl)ethyl vinyl ethers, F(CF2)nCH2CH2OCHCH2, (n = 6 or 8), were synthesized and polymerized by means of cationic initiators (HI/ZnI2 and CF3SO3H/(CH3)2S). The perfluorohexyl-substituted poly(vinyl ether) is completely amorphous. The polymer with perfluorooctyl segments shows side chain crystallization with a disordering transition. For the corresponding perfluorooctyl monomer a liquid-crystalline phase was observed before melting. Copolymerization experiments of the flurocarbon-segmented monomers with a vinyl ether containing a cyanobiphenyl group in the side chain did not give homogeneous copolymers. This is attributed to the slower rate of polymerization of the fluorinated vinyl ethers as compared with the liquid-crystalline comonomer.