SUMMARYThe influence of the components of an acidic solution: Cr(III) nitrate-malonic acid-Co(II) salt and treatment conditions on zinc dissolution and formation of Chromate films as well as on their decorative and protective properties have been studied using the analytical, XPS, structural and accelerated corrosion test methods. An organic acid is the main component, which has an essential influence on zinc dissolution and formation of Chromate films as well as their decorative and protective properties. The influence of organic acid is directly related with the state of the Cr3+ ions in chromating solution. When the Cr3+ ions are in the form of hexaaquaions, the organic acid increases the quantities of the zinc dissolved and the Cr(III) deposited on the zinc surface (especially at 60°C). It also predetermines the formation of a thick, porous Chromate film with large cracks at 60°C. Its decorative and protective properties are rather poor. When Cr3+ ions are in the form of a complex with organic acid, the quantities of the zinc dissolved and the Cr(III) deposited on the zinc surface significantly decrease and thinner Chromate films with an even surface, good decorative appearance and high corrosion resistance are formed Decorative blue-bright Cr(VI)-free films with a slight iridescent tint, obtained in solution, containing Cr(III) nitrate (0.2), malonic acid (0.3) and Co(II) nitrate (0.02) mol dm−3, at p H 1.6-2.0 at room temperature over 30–60 s, possess corrosion resistance (192–240 h in a salt spray chamber) similar to that of iridescent Chromate films, obtained in acidic Cr(VI) solution.