The work aims to prepare an anti-corrosion and environment-friendly Zirconium-Titanium/Silane composite film on magnesium alloy and investigate its corrosion properties. A conversion technology based on zirconium salt and titanium salt was combined with green organosilane technology to prepare the anti-corrosion and environment-friendly Zirconium-Titanium/ Silane composite film on the AZ31 magnesium alloy by immersing into the inorganic solution containing zirconium salt, titanium salt and tannic acid and then into the organosilane solution containing 5% volume concentration of bis-(γ-triethoxysilylpropyl)-tetrasulfide. The microstructure and element composition of the composite film were observed and analyzed by scanning electron microscope (SEM) and energy dispersive spectrometer (EDS). The corrosion resistance of the film was evaluated by polarization curves and electrochemical impedance spectroscopy. After the complex treatment by different Zirconium-Titanium/Silane, the Zirconium-Titanium/Silane composite film formed on the surface of the magnesium alloy showed homogeneous, flat, and some dry-riverbed-like nanoscale microcracks and had good corrosion resistance. Compared with the blank magnesium alloy, the minimum corrosion current density of the treated samples reached 1.51 μA/cm2, the corrosion rate was about 1/50 that of the blank sample, the electrochemical impedance spectroscopy was increased by 20 times at most and the maximum positive shift of the corrosion potential was close to 100 mV. The Zirconium-Titanium/Silane composite film has a significant physical barrier effect on the corrosive medium and obviously inhibits the dissolution of magnesium, blocks the electrochemical reaction process on the surface of the magnesium alloy, and reduces the corrosion rate of the magnesium alloy.