Adding nano particles can significantly improve the mechanical properties and wear resistance of thermal sprayed Al₂O₃ coating. However, it still remains a challenge to uniformly incorporate nano particles into traditional coatings due to their bad dispersibility. In the present work, nanometer Al₂O₃ (n-Al₂O₃) powders modified by KH-560 silane coupling agent were introduced into micrometer Al₂O₃ (m-Al₂O₃) powders by ultrasonic dispersion to afford nano/micro composite feedstock, and then four resultant coatings (weight fraction of n-Al₂O₃: 0%, 3%, 5% and 10%) were fabricated by atmospheric plasma spraying. The features and constitutes of feedstock and as-sprayed coatings, as well as their porosity, bonding strength, microhardness and frictional behaviors were investigated in detail. Results show that the nano/micro composite feedstock with uniform microstructure can be better melted in the spraying process, thereby obtaining coatings with denser microstructure, higher hardness and bonding strength. Added n-Al₂O₃ has no obvious effect on the friction coefficient of composite coatings, whereas can improve their wear-resistant and reduce the worn degree of counterpart. The wear mechanism of traditional coating is brittle fracture and lamellar peeling, while that of composite coating with weight fraction of n-Al₂O₃ of 10% is adhesive wear.