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A zinc/silicon dioxide composite film has been electrodeposited on carbon steel surface via adding tetraethylorthosilicate (TEOS) in zinc nitrate solution. The advantage of this method is that the metal/inorganic composite film can be fabricated without adding solid particles in solution. Polarization curve results showed that the composite film obtained at a TEOS concentration of 0.012 M had the best corrosion resistance. Electrochemical impedance spectroscopy results indicated that this film had a corrosion protection effect in 3.5 wt% sodium chloride solution for hundreds of hours. This kind of composite film can be potentially applied as anti‐corrosion coating for metal corrosion protection.