The presented contribution aims at investigating the role of nano-TiO2 dispersibility in affecting the performance of PVDF-HFP based composite polymer electrolytes (CPEs) for Li-ion cells. Four types of polymer electrolytes containing pristine PVDF-HFP gel polymer electrolyte (GPE), PVDF-HFP/nano-TiO2 CPE, PVDF-HFP/nano-TiO2-PMMA CPE and PVDF-HFP/high-dispersed nano-TiO2-PMMA CPE membranes are obtained by phase inversion. The effect of nano-TiO2 dispersibility on performances of PVDF-HFP based CPEs in terms of ionic conductivity, C-rate and cycling performance is investigated. The results demonstrate that the dispersibility of nano-TiO2 is a key factor to affect the performance of PVDF-HFP based CPEs, and the improvement of the dispersibility of nano-TiO2 can remarkably enhance the electrochemical performances of cells assembled with the corresponding CPEs.