This paper describes the preparation and thermal properties for homologous series of 2-oxochromen-6-yl 4-(4-alkoxyphenylazo)benzoates (compounds 1-n). Compounds 1-n show nematic phase exclusively, where the nematic-isotropic phase transition temperatures are between 293 degrees C for 1-4 and 256 degrees C for 1-8. Interestingly, compound 1-8 exhibits smectic A and re-entrant nematic phases in addition to the nematic one. The smectic A phase are characterized using a small angle X-ray diffraction study, indicating the smectic A phase has a partially bilayer molecular arrangement.