Synthesis and thermal properties of omega-[2-(4-X-phenoxycarbonyl)phenoxycarbonyl)-5-alkoxyphenoxy]alkyl and omega-[2-(4-X-phenoxycarbonyl)-5-alkoxyphenoxyalkyl poly-acrylates (X = n-alkoxyl or cyano group) have been reported. The homologs show a nematic phase, and a smectic phase as well as the nematic one is also formed when both terminal alkoxy chains of the core moiety are suitably long. On the cooling process, all the derivatives form a glassy phase corresponding to the prestates. The results will be discussed in terms of the molecular structure.