Organocobalt poly(arylene-vinylene)s composed of 1,2- or 1,3-linkage at their cyclobutadiene moieties (3 and 4, respectively) were prepared by the Heck reaction of p-divinylbenzene with (cyclobutadiene)cobaIt-containing monomers having two aryl bromide moieties (1 and 2,, respectively). The number average molecular weights (M-n) of the obtained organocobalt poly(arylene-vinylene)s (3 and 4) were 4,100 and 4,000, respectively (GPC, on the basis of polystyrene). UV-vis spectra of 3 and 4 exhibited main pi-pi* absorption peaks at 362 and 397 nm, respectively, which were ca. 60 nm bathochromically shifted from those of the corresponding monomeric units. Both polymers were found to show thermotropic liquid crystallinity in the range of room temperature to ca. 80 degrees C by employing differential scanning calorimetry (DSC) and the optical measurement using crossed polarizers.