Phosphate-manganese, tannic acid and vanadium conversion coatings were proposed as an effective pre-treatment layer between electroless Ni-P coating and AZ91D magnesium alloy substrate to replace the traditional chromate plus HF pre-treatment. The electrochemical results show that the chrome-free coatings plus electroless Ni-P coating on the magnesium alloy has the lowest corrosion current density and most positive corrosion potential compared with chromate plus electroless Ni-P coating on the magnesium alloy. These proposed pre-treatment layers on the substrate reduce the corrosion of magnesium during plating process, and reduce the potential difference between the matrix and the second phase. Thus, an electroless Ni-P coating with fine crystalline and dense structure was obtained, with preferential phosphorus content, low porosity, good corrosion-resistance and strengthened adhesion than the chromate plus electroless Ni-P.