Highly aligned polyacetylene films are synthesized by three different methods in which nematic liquid crystals are used as an ordered matrix solvent: Method 1, polymerization of acetylene is carried out in a quiescent nematic solution in which a Ti(OBu)4-AlEt3Ziegler-Natta catalyst is dissolved homogeneously; Method 2, macroscopic alignment is attained by gravity flow of the nematic liquid crystal-catalyst system; and Method 3, the nematic liquid crystal-catalyst solution is aligned under a magnetic field. Characterization of these films is carried out through SEM observation and measurements of polarized visible and infrared absorption spectra. Results indicate that as-prepared films have highly aligned fibrils. Upon doping by I2and AsF5, these films exhibit high electrical condactivity of the order of 104S/cm.