Alternating polyols of oxymethylene and oxyalkylene were synthesized and used as precursors for thermoplastic poly(ether-ester) elastomers (TPEs). The polyols were synthesized by reacting diols having different methylene units with dichloromethane in the presence of a phase transfer catalyst. The number of methylene units in the alkylene oxides was varied from 3 to 6. TPEs were prepared using the polyols as soft segments and poly(butylene terephthalate) units as hard segments. The polyols and TPEs synthesized were characterized using FTIR, NMR, GPC, DSC, and polarized optical microscopy. The polyols showed a profound odd-even effect on the melting (Tm) and glass transition temperatures (Tg). Polyols with odd numbers of methylene groups in the alkylene units have higher transition temperatures than polyols with odd number of methylene groups. The tendency is still kept in TPEs, even though the Tgs of soft segment in TPEs are slightly higher than those of corresponding neat polyols. The Tm and Tg of soft segments are almost constant in the range of 20 to 60 wt % contents of soft segments. On the other hand, the normalized heat of fusion of hard segment decreased with increasing the content of soft segment.