We report on the film formation of surfactant-free, artificial latexes based on copolymers containing maleic anhydride. Different metallic substrates, such as aluminum, steel and magnesium alloys, were coated with three different latexes. A commercial polyester based coating was used as a comparative sample. Two of the latexes were based on polymer with a high Tg (resp. ∼100 and 130 °C), and one on a polymer with a Tg of −70 °C. The wetting of the substrates could be optimized by etching the metal substrate, acidic or alkaline, leading to homogenous film formation and improved adhesion. For aluminum substrates an alkaline pretreatment improved the adhesion with the polymer films, whereas for magnesium the acidic pretreatment improved the adhesion. Furthermore, acid pretreatment increased the corrosion resistance of the coated magnesium substrate, when compared to an alkaline pretreatment. The films formed from latex displayed comparable or better anti-corrosive properties when compared to the commercial polyester.