Functionalized TiO2 (f-TiO2) was synthesized by the atom transfer radical polymerization process and then three types of composite nanofiber membranes including PI/PVdF-HFP (PI/PH, with no nanoparticles contained in PI), TiO2@PI/PVdF-HFP (T@PI/PH, with TiO2 mixed in PI) and f-TiO2@PI/PVdF-HFP (f-T@PI/PH, with f-TiO2 blended in PI) were prepared by bicomponent co-electrospinning technique which could separately maintain the original properties of both PVdF-HFP and PI nanofibers. UV–vis characterization manifested that the modified nanoparticles can provide significant improvements in reducing the particle agglomeration. Morphology, porosity, electrolyte uptake and liquid electrolyte contact angle of all the electrospun separators were investigated, and results showed that the composite separator with 2% f-TiO2 nanoparticle had smaller fiber diameter, higher porosity, larger electrolyte uptake, smaller contact angle and more excellent thermal dimensional stability. More importantly, the tensile strength of all the composite membranes increased by more than three times after thermal calendering process, which resulted from the several bonded points caused by the fusion of PVdF-HFP component with low melting temperature. Additionally, electrochemical properties of PI/PH, 2% T@PI/PH and 2% f-T@PI/PH composite separators and cycling performances of corresponding batteries were evaluated and 2% f-T@PI/PH composite separator showed better properties than the other two.