We first prepared an unsaturated epoxy resin ester (EM) by addition–esterification reaction with acrylic acid and then synthesized a series of acrylic ester/epoxy hybrid latexes (AE) with core–shell structure by semicontinuous emulsion polymerization method. The resultant AE emulsions are utilized as anticorrosion coatings of metals. The influences of EM content and crosslinking agent (PEG(400)DA) content on the physicochemical properties of the resultant emulsions and anticorrosion coatings of metals are investigated in detail. The AE emulsion displays better anticorrosion properties when it is prepared under the following conditions: the EM content of 30 wt% and PEG(400)DA content of 2.0 wt%. The relationships between the AE structure and anticorrosion properties of AE coatings are clearly illustrated. The corrosion resistances of AE coatings are not only depend on the crosslinking density, hydrophilic, and polarity among the AE chains, but also rely on the stability of the emulsion and the integrality and homogeneity of the coatings.