The high performance gel polymer electrolytes (GPEs) based on remarkable heat-resistant composite nanofiber membrane composed of polyetherimide (PEI) and halloysite nanotubes (HNTs) were obtained through the activation of stacked membranes immersed into liquid electrolyte. The crystallization behavior, microstructure and thermal stability of nanofiber membranes were analyzed. The HNT/PEI composite nanofiber membranes showed the sufficient porosity and good affinity between the nanofibers and the electrolyte as well as the electrode, which led to a superb saturated electrolyte uptake and conservation rate. Thus, the GPEs involving the HNT/PEI composite nanofiber membranes displayed excellent electrochemical performances, such as high ionic conductivity, adequate lithium-ion transference number, good interfacial stability and cycle performance. In particular, the GPEs based on 1wt% HNT/PEI nanofiber membranes demonstrated high ionic conductivity of 5.30×10−3 Scm−1 and low interfacial resistance of 180Ω. In addition, in contrast with the Li/GPE/LiCoO2 cells containing the commercial Celgard 2500, the assembled cells with the 1wt% HNT/PEI nanofiber membranes possessed outstanding initial discharge capacity, cycle performance and C-rate capability. Consequently, the GPEs involving HNT/PEI heat-resistant skeleton materials can satisfy the high-performance requirements of energy storage devices.