Highly stereospecific polymerization of a novel sulfur containing aromatic acetylenes, that is, (p-n-octylthiophenyl)acetylene (pOctSPA), was successfully performed using the Rh complex, [Rh(norbornadiene)Cl](2)-TEA, catalyst in the presence of various solvents under mild conditions. The resulting polymers were characterized in detail by H-1 NMR, ESR, laser Raman, diffuse reflective UV-Vis (DRLTV-Vis), and wide angle X-ray diffraction methods. The data showed that the resulting polymers bear cis-transoid form, which can induce the cis-to-trans isomerization when the cis polymers are subjected to pressure at room temperature under vacuum, breaking rotationally the cis C=C bonds in the main-chain giving two kinds of pi-radicals, the so-called cis radical and trans radical as the origin of a polymer magnet like a novel spin glass material. Further, the resulting cis poly(acetylene)s were found to have a helical main-chain, which is packed in pseudohexagonal crystal called T-conjugated columnar or nano pi-conjugated columnar as a novel color controllable material. (c) 2005 Wiley Periodicals, Inc.