The invention discloses a steel mill continuous annealing galvanized sheet chromium-free compound passivator which comprises the following raw materials in percentage by weight: 5-20 percent by weight of a main film-forming agent, 0.1-5 percent by weight of a coupling agent, 0.1-0.5 percent by weight of inorganic complex film-forming agent, 0.1-4 percent by weight of silicate, 0.1-0.4 percent of an emulsifying agent, 0.1-0.2 percent of a dispersing agent, 0.1-0.4 percent of a corrosion inhibitor, 0.1-0.3 percent of a protective colloid, 0.1-1 percent of a nanometer sealing agent, 0.1-0.4 percent of phosphate and the balance of water. The steel mill continuous annealing galvanized sheet chromium-free compound passivator disclosed by the invention is uniform in appearance, stabilizes a liquid, has an expiration date of above 90 days, is nontoxic and environment-friendly, and accords with the ROHS (Restriction Of Hazardous Substances) requirement. The steel mill continuous annealing galvanized sheet chromium-free compound passivator is simple in preparation process; a passivated film is uniform in appearance and has certain glossness. A galvanized sheet passivated by using the passivator has the advantages that the corrosion resistance is remarkably improved, the neutral salt mist SST (Sea Surface Temperature) resistant time reaches above 72 hours, the white rust area is less than 5 percent, the blackening resistance delta E is less than 5, the yellowing resistance delta E is less than 3, the alkaline resistance delta E is less than 3, the interlamination resistance R is less than 3 omega/cm, and the conductivity is less than 1 m Omega.