Nanofibers fabricated by the electrospinning process have been used to construct sandwich-type Polyimide/Poly (vinylidene fluoride)/Polyimide (PI/PVDF/PI) separators with the thermal shutdown function for lithium ion batteries. This architecture uses the good thermal stability of PI as the top and bottom structure layers. Under high temperature operations, the middle layer made of PVDF nanofibers can melt and form a pore-free film to shut down the battery operation. The electrolyte uptake and ionic conductivity of the PI/PVDF/PI separator are superior to those of commercial polyolefin separators at 476% and 3.46mScm−1, respectively, resulting better battery performances in terms of impedance, discharge capacity and cycle life. Under high temperature treatments above 170°C, the self-shutdown function of the PI/PVDF/PI has been observed within 10minutes, which could serve as the safety mechanism to defend the thermal runaway issue of lithium ion batteries. The effects of heating temperature and different time on the morphologies of each layer and electrolyte uptake of the separator are characterized as well.