Polypropylene (PP)/polyethylene (PE) multilayer separators with cellular-like submicron pore structure for lithium-ion battery are efficiently fabricated by the combination of multilayer coextrusion (MC) and thermal induced phase separation (TIPS). The as-prepared separators, referred to as MC-TIPS PP/PE, not only show efficacious thermal shutdown function and wider shutdown temperature window, but also exhibit higher thermal stability than the commercial separator with trilayer construction of PP and PE (Celgard (R) 2325). The dimensional shrinkage of MC-TIPS PP/PE can be negligible until 160 degrees C. In addition, compared to the commercial separator, MC-TIPS PP/PE exhibits higher porosity and electrolyte uptake, leading to higher ionic conductivity and better battery performances. The above-mentioned fascinating characteristics with the convenient preparation process make MC-TIPS PP/PE a promising candidate for the application as high performance lithium-ion battery separators.