Liquid crystalline polyethers have been synthesized from 1-(4-hydroxy-4’-biphenylyl)-2-(4-hydroxyphenyl)propane and alpha,omega-dibromoalkanes with even-numbers of methylene units [TPP(n = even)s]. Multiple phase transitions are found during cooling and heating via differential scanning calorimetry (DSC), and they show little undercooling dependence. Ordered structure identifications are based on experimental observations of wide angle X-ray powder and fiber diffraction experiments at different temperatures. Polarized light and transmission electron microscopy observations on mesophase morphology combined with DSC results on thermodynamic transition properties also provide additional evidence for these phase assignments. Moreover, the contributions of the mesogenic groups and the methylene units to each ordering process are obtained based on the changes of transition enthalpy and entropy. In TPP(n less than or equal to 8)s the highest temperature transition is from the isotropic melt to a nematic phase. This nematic phase is only stable in a narrow temperature range. For instance, it is 12 degrees C for TPP(n = 4) and 6 degrees C for TPP(n = 8). When the number of methylene units n greater than or equal to 10, the isotropic melt directly enters a smectic F phase. The second transition in TPP(n less than or equal to 8)s is from the nematic to the smectic F phase. As a result, the smectic F phase exists for all TPP(n = even)s. Decreasing the temperature further leads to another transition in TPP(n = even)s to form a smectic crystal G phase which is followed by a transition to a smectic crystal H phase. This smectic crystal H phase remains for TPP(n less than or equal to 8)s down to their glass transition temperatures, while in TPP(n greater than or equal to 10)s further ordering processes occur and crystal phases are observed. A phase diagram of TPP(n = even)s is constructed.