The work aims to explore nano-Al2O3/TiO2 spraying process, and study its mechanical properties emphatically. Nanostructured Al2O3/TiO2 ceramic coatings were fabricated on metallic surface in the method of atmospheric plasma spraying. Provided with permanent spraying current, spraying distance and powder feeder speed, thermal sprayed samples were prepared by applying four groups of process and adjusting main pressure intensity and spraying voltage, and the preparation technology was optimized. Bonding strength, microstructure, hardness, fracture toughness, cupping property and thermal shock resistance of the optimized coatings were characterized. Friction and wear properties of the nano-ceramic coatings in ball-disk mode were studied. The optimum process of spraying nano-ceramic coatings AT13 was determined by analyzing microhardness, crack resistance and fracture toughness data of the composite coatings. The bonding strength and hardness of nano-ceramic coatings were both high. The nanostructure in original coating was inherited from the coatings. The nano-coatings exhibited excellent cupping resistance, and better toughness than traditional micron coatings. After 50 cycles of water quenching at 400 ℃ to room temperature, no failure occurred in the coatings. During frictional wear of large load ball-disk, abrasion loss of nano-ceramic coatings was slight and friction coefficient was stable, the coatings showed good tribological properties. Nano-alumina titanium ceramic coatings feature in high bonding strength, excellent cupping resistance, wear resistance and good overall general mechanical performance, hence they are applicable to harsh working environment.