Duty ratio is a key factor during micro-plasma oxidation process. Its influences on structure and corrosion resistance of ceramic coatings on Ti–6Al–4V by pulsed bi-polar MPO in NaAlO2 solution were investigated. The ceramic coatings were composed of Al2TiO5, α-Al2O3 and rutile TiO2, of which Al2TiO5 was the main crystalline. The coating can be divided into a porous outer layer and a dense inner layer. Compared with the condition of the same duty ratio for both pulses, the rise of anode duty ratio (D1) led to an increase in the amount of Al2TiO5 and α-Al2O3 and increased the thickness of the coating; whereas the rise of cathode duty ratio (D2) led to a decrease in the amount of α-Al2O3 and decreased the thickness of the coating. Besides, the corrosion resistance of the coated samples was better than that of Ti-6Al-4V substrate. When D1 / D2 = 60 / 30, the produced coating’s corrosion resistance was best.