To improve the thermal shrinkage of the separators that are essential to securing the electrical isolation between electrodes in lithium-ion batteries, we develop a new separator based on a ceramic composite membrane. Introduction of microporous, ceramic coating layers onto both sides of a polyethylene (PE) separator allows such a progress. The ceramic coating layers consist of nano-sized alumina (Al2O3) powders and polymeric binders (PVdF-HFP). The microporous structure of the ceramic coating layers is observed to be crucial to governing the thermal shrinkage as well as the ionic transport of the ceramic composite separators. This microporous structure is determined by controlling the phase inversion, more specifically, nonsolvent (water) contents in the coating solutions. To provide a theoretical basis for this approach, a pre-investigation on the phase diagram for a ternary mixture comprising PVdF-HFP, acetone, and water is conducted. On the basis of this observation, the effect of phase inversion on the morphology and air permeability (i.e. Gurley value) of ceramic coating layers is systematically discussed. In addition, to explore the application of ceramic composite separators to lithium-ion batteries, the influence of the structural change in the coating layers on the thermal shrinkage and electrochemical performance of the separators is quantitatively identified.