Shape-tunable hydroxyl copolyimide (HPI) nanoparticles are fabricated by a re-precipitation method and are coated onto electrospun HPI membranes, followed by heat treatment to prepare thermally rearranged polybenzoxazole (TR-PBO) composite membranes. The morphology of HPI nanoparticles consisted of sphere and sea-squirt structures, which is controlled by changing the concentration of the stabilizer. The morphological characteristics of TR-PBO nanoparticles convert from HPI nanoparticles by heat treatment and their composite membranes is confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (ATR-IR), thermogravimetric analysis (TGA) analysis, and contact angle measurements. TGA and DSC measurements confirm the excellent thermal stability compared to Celgard, a commercial PP separator for lithium-ion batteries (LIBs). Further, TR-PBO nano-composite membranes used in coin-cell type LIBs as a separator show excellent high power density performance as compared to Celgard. This is due to the fact that sea-squirt structured nanoparticles have better electrochemical properties than sphere structured nanoparticles at high temperature.