Poly(vinylidene fluoride)/polysulfone (PVDF/PSF) blend microporous matrix of polymer electrolyte for lithium ion battery is prepared via thermally induced phase separation (TIPS) technique. Because of only one parameter, i.e., the PSF/PVDF weight ratio, the membrane microstructure is conveniently controlled. The membrane formation mechanism of PVDF/PSF blend membranes is proposed with the assistance of a binary PSF/PVDF weight ratio-temperature phase diagram. In addition to studying the microstructure and mechanical properties of PVDF/PSF blend membrane, the relationship between properties of membrane, electrochemical performances of corresponding polymer electrolyte and membrane microstructure are also discussed in this paper. It is found that the addition of PSF not only increases ionic conductivity and electrochemical stable window of polymer electrolyte, but also markedly enhances charge–discharge performances of coin cell. The results reveal that PVDF/PSF blend microporous membranes prepared via TIPS technique can be used as polymer matrices of polymer electrolytes for lithium ion batteries.