A new class of fluorinated polymers was prepared by radical ring-opening homopolymerization of vinylcyclopropane monomers with a perfluorinated (CF2)(n)F chain (n = 6, 8, or 10). The polymers were in fact copolymers composed of 1,5-linear and cyclobutane isomer units, the relative content of which depended on n. Surprisingly, they formed liquid-crystalline mesophases (SmBd and/or SmA(d)), which was attributed to phase separation of the incompatible fluorocarbon and hydrocarbon components of the repeat unit.