The innovative work presented in the paper focused on microstructures and wear performance of MoS2 doped Al2O3 coatings on TC6 alloy. Nano- and micron-sized MoS2 particles doped Al2O3 coatings (n and m-MoS2/Al2O3 coating) were fabricated on TC6 alloy via cathodic plasma electrolytic deposition (CPED) technique. The microstructures and compositions of the coatings were characterized, the tribological behaviors were tested, and doping mechanism of MoS2 particles was discussed. The results showed that, doped coatings were composed of α-Al2O3, γ-Al2O3 and MoS2. The doping of MoS2 particles promoted the transformation from γ-Al2O3 to α-Al2O3 during CPED process, and increased the compactness and crystallinity of doped coatings. The friction coefficients of TC6 alloy, Al2O3 coating, n-MoS2/Al2O3 coating and m-MoS2/Al2O3 coating were about 0.7, 0.6, 0.55 and 0.45 in sequence, and the wear rates of n-MoS2/Al2O3 coating and m-MoS2/Al2O3 coating were about 75 % and 58 % of Al2O3 coating. MoS2 particles played the role of lubrication and contributed to improving wear performance of doped coatings, both friction coefficients and wear rates were declined, and micron-sized MoS2 particles presented better wear performance than nano-sized particles.