A group of mesomorphic polyacetylenes with different lengths of alkyl spacer -{HC=C[(CH2)(m)-OCO-Biph-OC7H15]}(n)-[1(m), m = 2, 3, 4, 9] and orientations of ester bridge - {HC= C[(CH2)(3)-CO2-Biph-OC7H15]}(n)-[2(3)] are synthesized, and the effects of the structural variables on the properties of the polymers are investigated. The liquid crystalline acetylene monomers n-{[(4'-heptoxy-4-biphenylyl)carbonyl]oxy}-1-alkynes 3(m) and 5-{[(4'-heptoxy-4-biphenylyl)carbonyl]oxy}-1-pentyne 4(3) are prepared by consecutive etherification and esterification reactions. The T-m and T-i values of 3(m) decrease with an increase in the spacer length (m). While 3(3) shows a monotropic SmA phase, its counterpart with a different eater orientation 4(3) exhibits an enantiotropic SmB phase. The monomers are polymerized by transition-metal halides and carbonyls, and the polymerizations catalyzed by WCl6Ph4Sn under optimal conditions produce polymers with high molecular weights (up to 1.2 x 10(5)) in high yields (up to 92%). The structures and properties of the polymers are characterized and evaluated by IR, UV, TCA, DSC, POM, and XRD analyses. With the increase in the spacer length, the thermal stability of the polymers increases, their T-g and T-i decrease, and the packing arrangements in their mesophases change from mixed mono- and bilayer structures to a homogeneous monolayer structure. Compared to 1(3), 2(3) shows a blue-shifted absorption spectrum (Delta lambda(max) > 30 nm), a higher T-g and T-i(Delta T similar to 40 degrees C), and a better packed SmA(d) structure.