We have synthesized novel mono-substituted acetylenes with a photoresponsive azobenzene group and then polymerized them with Ziegler-Natta, metathesis, and Rh based catalysts. Especially, the Rh catalyst containing chloroform as a solvent produced a cis rich polymer with high yield of 90%. Through the measurements of DSC and polarizing microscope : polymer with a n-pentyl azobenzene group was found to show a smectic liquid crystalline phase. The reversible photoisomerization of all monomers and polymers was generated due to the irradiation of a UV(350nm) or Visible(450nm) monochromatic light.