Solid polymer electrolytes (SPEs) have great potential to address the safety issues of lithium (Li)-ion batteries when compared with conventional liquid electrolytes, which makes them a promising alternative for next-generation high-energy batteries. In this work, poly(ethylene oxide)-lithium perchlorate (PEO-LiClO4) polymer electrolytes for Li-ion batteries were prepared using electrospinning. The crystallinity, ionic conductivity as well as mechanical properties were investigated. Ionic conductivities and mechanical properties of PEO-LiClO4 based SPE have been obviously increased by incorporating modified TiO2 nanofibres (TNFs) than TiO2 nanoparticles (TNPs), due to that both TNFs and TNPs can decrease the crystalline phase concentration of PEO and increase segmental flexibility of PEO. The SPE with 3 wt% TNFs exhibits the highest conductivity of 5.308 x 10(-5) S cm(-1) at 20 degrees C and higher tensile strength of 13.8 MPa. These results highlight the potential of utilising the electrospinning method to improve the ionic conductivity of SPEs.