An eco-friendly rust converter treatment based on tannic acid was optimized by orthogonal experiment, and the adhesion of the epoxy top-coating system was evaluated. The results showed that the adhesion between the epoxy coating and the rusted steel after treatment was enhanced from 1.93 to 5.97 MPa. This adhesion improvement was attributed to the formation of the micro-cracked tannic conversion layer and the increase of the compactness of the rust layer. The failure analysis suggested that the remainder rust was still the key issue for the further adhesion improvement of the coating system.