This paper reports on a new comb branch polymer based on trimethylene oxide (TMO) side chains as a polymer electrolyte for potential application in lithium metal rechargeable batteries. The trimethylene oxide (TMO) units are attached to the side chains of a polyepoxide ether to maximize the segmental motion. Lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) salt was used to formulate the polymer electrolyte with the new TMO containing polymers. The new polymer electrolytes show improved salt diffusion coefficients (Ds) and conductivity at ambient and subambient temperature compare to the ethylene oxide (EO) counterpart, whereas performance at high temperature (85 °C) remains the same or is actually worse for salt diffusivity.