Novel side-chain liquid crystalline polyacetylene derivatives were synthesized by polymerizing substituted acetylene monomers with Ziegler-Natta and metathesis catalysts. Liquid crystallinities of the monomers and polymers were examined by means of miscibility tests, polarizing microscope and DSC measurements. Feasibility of iodine doping to the polymers was confirmed through UV-Vis absorption and ESR measurements. Changes of electronic and geometrical structures of the polymers upon the iodine doping were elucidated in terms of conjugation length of polyene chain, cis and trans forms, and spin distribution of unpaired electrons.