The work aims to further improve corrosion resistance of chromium-free passive film on hot-dip galvanized steel. With H2TiF6 and NH4VO3 as proper inorganic constituents and styrene-acrylic emulsion as major film-forming material, a layer of corrosive bis-silane chromium-free passive film was obtained on hot-dip galvanized steel by binding the constituents tightly using silicon coupling agent (KH-560, KH-570). Corrosion resistance of the bis-silane chromium-free passive film was characterized by neutral salt spray test, electrochemical test, scanning electron microscopy and Fourier infrared spectroscopy. Corrosion area of the film accounted for approximately 2%~4% after 96 h neutral salt spray test, and corrosion current density was one order of magnitude lower than that of untreated hot-dip galvanized steel, indicating that the bis-silane chromium-free passive film could exhibit excellent corrosion resistance. SEM analysis showed that a nearly 3 μm thick uniform, continuous and compact passive film took shape on the surface of hot-dip galvanized steel. FTIR analysis indicated that —(CH2) n—, C＝O, Si—O, Si—O—Si and Si—O—Zn bonds were present in the passive film. The hot-dip galvanized steel exhibits excellent corrosion resistance and meets requirements of industrial application since a layer of uniform and compact passive film takes shape on the surface of hot-dip galvanized steel.