A novel composite nonwoven separator exhibiting high heat resistance, high ionic conductivity and high lithium ion transference number is fabricated by a simple dip-coating and heat treatment method. The thermal stable polyimide (PI) nonwoven matrix is chosen as a mechanical support and contributes to improving the thermal shrinkage of the composite nonwoven separator (abbreviated as IACS). The cross-linked poly(2-acrylamido-2-methylpropanesulfonic acid) PAMPS(Li+) gel polymer electrolyte (GPE), lithium ion sources of a single ion conductor, is introduced into the PI nonwoven matrix and acts as a functional filler. This PAMPS (Li+) GPE is proved to be able to provide internal short circuit protection, to alleviate liquid electrolyte leakage effectively, to supply more lithium ions dissociating from PAMPS (Li+) by liquid electrolyte solvent, to contribute a more stable interfacial resistance, and thus resulting in an excellent cyclability. More notably, the migration and mobility rate of anions could be hindered by the −SO3 − group in the PAMPS (Li+) polymer based on electrostatic interaction, giving rise to a very high lithium ion transference number. These fascinating characteristics endow the IACS a great promise for the application in the high power and high safety lithium ion batteries.