The invention relates to the technical field of 
metal passivators, and particularly relates to a 
chromium-free composite passivator and a preparation method thereof. The 
chromium-free composite passivator provided by the invention is prepared from the following components in percentage by 
mass: 3.0-10% of gamma-methylacryloyloxytrimethoxy 
silane, 0.1-3.0% of 
sodium molybdate, 0.1-5.0% of 
cerium chloride, 0.5-4.0% of 
phosphoric acid, 0.5-4.0% of 
acetic acid, 15-20% of water-soluble 
epoxy resin, 5-15% of water-soluble 
acrylic resin, 10-30% of water and 20-40% of 
ethanol. The 
chromium-free composite passivator is suitable for treating steel, 
zinc and 
zinc alloy, or aluminum and aluminum 
alloy. The chromium-free composite passivator contains the water-soluble high-molecular resins and inorganic 
corrosion inhibitor, and is mixed with 
ethanol to form a colorless, innoxious, environment-friendly, transparent and clear solution. At 
room temperature, the chromium-free composite passivator is applied on the surface of steel, hot-galvanized 
zinc and zinc 
alloy, or aluminum and aluminum alloy to generate chemical crosslinking reaction, and is cured to form a film.