The work aims to fabricate a new waterborne epoxy resin coating with low VOC and low toxicity. An aqueous epoxy resin emulsifier was prepared by reaction of epoxy E51 with N,N-dimethylethylenediamine and then neutralized to salt with glacial acetic acid obtain a reactive water-based epoxy emulsifier. Reactive water-based epoxy emulsifier was mixed with epoxy resin E51 and four types of amine-based curing agents (651, GT19, DL19, SG) based on certain proportion and then coated on the electrode surface and sealed after being cured to film. The structure of the emulsifier was characterized by Micro-FTIR spectrometer. The particle size of the emulsion obtained by emulsifying the emulsifier E51 was tested by a dynamic light scattering particle size analyzer (ZETA). Electrochemical impedance spectroscopy and polarization curve tests were conducted to study the corrosion resistance of four curing agent-cured waterborne epoxy coatings in 3.5% NaCl solution. When the mix proportion of emulsifier and E51 was 1∶1, the average size of emulsion was the minimum, distribution was uniform and the system was stable. The coatings obtained with 651 curing agent had the maximum hardness and the strongest adhesion. Cross-linking density was the highest and coating cross section was the densest. After immersed in 60 hours, the coating still had a higher impedance modulus value of 5.23×104 Ω×cm2 and a lower self-corrosion current density of 2.0×10-7 A/cm2, thus exhibiting significant anti-corrosion properties for the base carbon steel. The prepared waterborne epoxy resin coating has good protective performance for the steel substrates and is suitable for the field of environment-friendly low VOC coatings.