A series of new thermotropic main-chain liquid crystalline copolyesters were prepared by polycondensation of 2,6-naphthalenedicarbonyl chloride, 4,4Ј-thiodiphenol, and ␣,-alkanediols (n ϭ 4 -10) in diphenyl ether at 200°C. Thermal transition behaviors of these copolyesters were investigated by differential scanning calorimetry. Moreover, their thermal stabilities and mesomorphic textures were studied by thermogravimetric analysis and polarizing optical microscopy, respectively. Corresponding model compounds with terminal mesogenic units and central polymethylene spacers were also synthesized for comparison. Both copolymers and model compounds exhibit odd-even dependency of melting temperatures, transition enthalpy (⌬H m ), and entropy (⌬S m ) on the number of methylene units in the spacer. However, the odd-even effects in model compounds are much more distinctive. Nematic mesophases are the only texture observed in melts, except the model compounds with longer methylene units (n ϭ 8, 10), in which smectic mesophases can be observed. The T m values of the copolyesters (TDP/HD ϭ 1/1) are between 233 and 259°C, depending on spacer length. The initial decomposition temperatures of the copolyesters are above 419°C under N 2 atmosphere.