AbstractTwo kinds of phosphate conversion coatings, including zinc phosphate coating and zinc–calcium phosphate coating, were prepared on the surface of AZ31 alloy in phosphate baths. The morphologies of these coatings were observed using scanning electron microscopy. Their chemical compositions and structures were characterized using energy-dispersive X-ray spectrum, X-ray photoelectron spectroscopy and X-ray diffraction. The corrosion resistance of the coatings was evaluated by potentiodynamic polarization technique. The results show that the flowerlike Zn–Ca phosphate conversion coatings are mainly composed of hopeite (Zn3(PO4)2·4H2O). They have a quite different morphology from the dry-riverbed-like Zn phosphate coatings that consist of MgO, MgF2, Zn or ZnO and hopeite. Both of the zinc and zinc–calcium phosphate coatings can remarkably reduce the corrosion current density of the substrates. The Zn–Ca coating exhibits better corrosion resistance than the Zn coating. Introduction of calcium into the phosphate baths leads to the full crystallinity of the Zn–Ca coating.