In this work, a side-by-side bicomponent thermoplastic polyurethane/polyimide (TPU/PI) polymer electrolyte prepared with side-by-side electrospinning method is reported for the first time. Symmetrical TPU and PI co-occur on one fiber, and are connected by an interface transition layer formed by the interdiffusion of two solutions. This structure of the as-prepared TPU/PI polymer electrolyte can integrate the advantages of high thermal stable PI and good mechanical strength TPU, and mechanical strength is further increased by those isotropic interface transition layers. Moreover, benefiting from micro-nano pores and the high porosity of the structure, TPU/PI polymer electrolyte presents high electrolyte uptake (665%) and excellent ionic conductivity (5.06 mS·cm-1) at room temperature. Compared with PE separator, TPU/PI polymer electrolyte exhibited better electrochemical stability, and using it as the electrolyte and separator, the assembled Li/LiMn₂O₄ cell exhibits low inner resistance, stable cyclic and notably high rate performance. Our study indicates that the TPU/PI membrane is a promising polymer electrolyte for high safety lithium-ion batteries.