In a variety of engineering applications, components are subjected to corrosive environment. Protective coatings are essential to improve the functional performances and/or extend the lifetime of the components. Thermal sprayingas a cost-effective coating deposition technique offers high flexibility in coatings' chemistry/morphology/microstructure design. However, the inherent pores formed during spraying limit the use of coatings for corrosion protection. The recently developed supersonic spray method, High-Velocity-Air-Fuel (HVAF), brings significant advantages in terms of cost and coating properties. Although severely reduced, the pores are not completely eliminated even with the HVAF process. In view of the above gap to have a high quality coating, bi-layer coatings have been developed to improve the corrosion resistance of the coatings. In a bi-layer coating, an intermediate layer is deposited on the substrate before spraying the coating. The electrochemical behavior of each layer is important to ensure a good corrosion protection. The corrosion behavior of the layers strongly depends on coating composition and microstructure, which are affected by feedstock material and spraying process. Therefore, the objective of the researchis to explore the relationships between feedstock material, spraying process, microstructure and corrosion behavior of bi-layer coatings. A specific motivationis to understand the corrosion mechanisms of the intermediate layer which forms the basis for developing superior protective coatings. Cr3C2-NiCr top layer and intermediate layers (Fe-, Co- and Ni-based) were sprayed by different thermal spraying processes. Microstructure analysis, as well as various corrosion tests, e.g., electrochemical, salt spray and immersion tests were performed. The results showed a direct link between the corrosion potential (Ecorr) of the intermediate layer and the corrosion mechanisms. It was found that the higher corrosion resistance of Ni-based coatings than Fe- and Co-based coatings was due to higher Ecorr of the coating in the galvanic couple with top layers. Inter-lamellar boundaries and interconnected pores reduced the corrosion resistance of intermediate layers, however a sufficient reservoir of protective scale-forming elements (such as Cr or Al) improved the corrosion behavior.