Inspired by the ingenious architecture of nacre and its outstanding mechanical properties, we prepared nanoscale ceramic (TiC, Si3N4, B4C) /Teflon multilayers by ion beam sputtering deposition at room temperature. The toughness, hardness and tribological properties were systematically investigated as well as the multilayer structures. It was found that the toughness of ceramic/Teflon multilayers were all significantly improved in comparison with the corresponding monolithic ceramic material, but the hardness was decreased. However, there were optimized layer thickness arrangements with which the multilayer toughness and hardness can be favorably combined to obtain better comprehensive properties. It was found by this study that ceramic/polymer multilayers with the optimized layer thickness arrangement had good performance in wear resistance.