A new chromium-free conversion film was obtained on surface of a ZnAl alloy by chemical conversion process.Influence of the additives in treating solution containing cerium salt on the corrosion protection of the conversion film formed on zinc alloy was investigated. Corrosion tests and electrochemical measurements in sodium chloride solution were performed. The microstructure and composition of the coatings were examined by means of SEM, EDS and XRD. It was found that the corrosion protection capabilities of the conversion film are markedly increased with the cerium nitride plus additives (hydrogen fluoride acid and an organic inhibitor) treating process. The modified conversion film is an organic/inorganic composite coating and is much more corrosion resistant than the conventional chromate conversion coating and the single cerium conversion coating.