AbstractCationic bulk polymerization of liquid crystalline phenyl benzoate and biphenyl vinyl ethers was performed using either thermal or photochemical initiation by onium salts. High molecular mass polymers having narrow molecular mass distribution were produced in high yields at very high temperatures (i.e., ≤ 120°).Seemingly, the polymerization system could stabilize the growing species and thus reduce the amount of chain transfer reactions. Thin films of the monomers were oriented in their liquid crystalline state by the use of conventional ordering techniques used for low molar mass liquid crystals. On subsequent polymerization the orientation was preserved giving liquid crystalline thin films having a very high degree of ord