One way to obtain the lithium ion power battery with better safety performance was to increase the thermal shrinkage resistance of the separator at higher temperature. Phenolphthalein polyetherketone (PEK-C) is a polymer that can withstand high temperature to about 230°C. Here, we developed a new Al2O3 coated composite polypropylene (PP) separator with PEK-C as binder. The coating layer was formed on the surface of the PP separator and both ceramic particles and binder did not infiltrated into the separator along the thickness direction. The composite separator with 4μm coating layer provided balanced permeability and thermal shrinkage properties. The composite separator was stable at the electrochemical window for lithium ion battery. The coin cells with composite separator showed better charge/discharge performance than that of the cells with the PP separator. It seemed that the composite separator was helpful for high current density discharge. Also, the battery safety performance test had verified that the Al2O3 coated composite separator with PEK-C as binder had truly improved the safety performance of the coin cells. So, the newly developed Al2O3 coated composite PP separator was a promising safety product for lithium ion power batteries with high energy density.