<p>The replacement of harmful chromate-based corrosion inhibitors is an important topic to provide a more environmentally friendly approach in corrosion science. In this work, we combined zinc vanadate and zinc phosphate to develop a novel, highly effective anti–corrosion pigment which was synthesized through a simple co-precipitation method with the ratio of zinc vanadate to zinc phosphate varying from 95:5 to 85:15 by weight. Steel specimens were coated with epoxy integrated with the pigments, exhibiting a significant decrease in corrosion current density. The coupling of zinc phosphate and zinc vanadate improved the corrosion resistance of the coating. The optimal formulation was obtained with the ratio of zinc vanadate to zinc phosphate being 85:15. After 3&#xa0;days of immersion in 3.5% NaCl solution, the corrosion current density of the steel specimens containing this pigment was 4 times lower than those of the samples containing only zinc phosphate or zinc vanadate. A mechanism was also proposed to illustrate the synergistic effects of corrosion inhibition in binary pigments systems. This mechanism involves with the initial formation of phosphate–based passivation film, after which the vanadate–based species would “heal” the defective sites. This creates a better barrier, decreasing the penetration of corrosive species. The proposed mechanism provides opportunities for further work to explore insights into passivation films formation.</p>