: The internal short-circuit between cathodes and anodes has been known to be a critical concern for the safety failures of lithium-ion batteries, which is strongly influenced by the thermal stability of separators. In this study, to effectively suppress the internal short-circuit failures, we developed a new composite separator with the improved thermal stability compared to conventional polyolefin-based separators. The composite separators were prepared by introducing a ceramic coating layer (Al 2 O 3 /PVdF-HFP) onto both sides of a polyethylene (PE) separator. The microporous structure of ceramic coating layers is determined by controlling the phase inversion of coating solutions and becomes more developed with the increase of nonsolvent (water) content. This structural change of ceramic coating layers was observed to greatly affect the thermal stability as well as the electrochemical performance of composite separators, which was systematically discussed in terms of phase inversion.