A series of liquid crystal (LC) PB-8/12 copolyesters have been synthesized from 4,4′-biphenol with sebacic acid and tetradecanedioic acid, and their LC structures and morphologies have been examined. The copolyesters formed smectic I (SmI) LCs similarly as to the corresponding PB-8 and PB-12 homopolyesters; however, dissimilarity of the comonomer lengths decreased the smectic layer order while sustaining the hexagonal order in the lateral packing of the chains. The SmI LCs consisted of 100-nm-thick lamellae stacked along the polymer chain direction. The lamella thicknesses are more than two times greater than the thicknesses of the homopolyesters and comparable to or greater than the chain contour lengths, indicating the formation of extended chain lamellae.