Fabricating flexible composite polymer electrolytes (CPEs) with vertically aligned ion transport pathways is necessary for the application of solid-state lithium metal batteries (LMBs), yet the orientation of polymer matrix usually is disorder, thus the improvement in ionic conductivity is unsatisfied. Herein, we develop a simple electric field induced molecular orientation strategy to fabricate the flexible CPEs with vertically aligned ion transport pathways. Driven by direct current (DC) electric field (e.g. 1.5 MV m−1), the polar 15C5-Li+ dipoles and monomer molecules are oriented regularly and cured to form flexible three dimension (3D) cross-linked structure. As a result, numerous vertically-aligned ion transport pathways have been generated in the vertically oriented arrangement CPEs, thus presenting highly enhanced ionic conductivities, mechanical strength and superb inhibition ability to lithium dendrite growth. When used as CPEs for Li||LiFePO4 (LFP) batteries, the vertically oriented CPEs exhibit excellent rate and long-term cycle stability with a reversible discharge capability of 124.9 mAh g−1 after 350 cycles at 1C and 60 °C. However, the randomly oriented CPEs deliver much poor cycle and rate performance at the same conduction. It can also be compatible with NCM811|Li batteries at 30 °C. Therefore, our simple DC electric field induced molecular orientation strategy holds a great application promise to construct the fast ion transport channels for the all-solid-state LMBs.