Based on our differential scanning calorimetry observations, a polyether 1 synthesized from 4'-[2-(4-hydroxyphenyl)propyl]-4-biphenylol and 1,9-dibromononane shows multiple transition behavior during cooling and heating. Furthermore, these transition temperatures do not exhibit significant supercooling dependence. Detailed analyses of the wide-angle Xray diffraction powder and fiber patterns at different temperatures have indicated that highly ordered smectic F and G phases exist in this polyether and are differentiated from traditional crystalline phases.