This paper describes thermal properties and molecular arrangements for alpha, omega-bis(3-nitro-4-(2-perfluorooctyl)ethoxybenzoyloxy)alkanes. The homologous series shows a smectic A (SmA) phase as well as higher ordered smectic one, and the layer structure of the SmA phase is examined by X-ray diffraction. The phase transition behavior and layer structure are notably influenced by the central alkylene chain length. These results are compared with those for the corresponding monomeric liquid crystals.