In this study, FeCrMnWMoSi amorphous/nanocrystalline coating was prepared on stainless steel by high-velocity oxygen fuel (HVOF) spraying. In order to thoroughly evaluate this novel material, the corrosion behaviors and corrosive film characteristics of the amorphous/nanocrystalline coating in NaCl corrosive media were studied using electrochemical measurement technologies such as potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). It was found that the corrosion resistance of Fe-based amorphous/nanocrystalline coating could be attributed to the passive film formed, which consisted of Fe, Cr, Mo, and W oxides. pH has an important influence on the corrosion resistance of amorphous/nanocrystalline coating by changing the pitting corrosion mechanism. Under neutral and acidic conditions, the corrosion mechanism of Fe-based amorphous/nanocrystalline coating was mainly local pitting corrosion. However, under strong alkaline conditions, the amorphous/nanocrystalline coating not only had pitting corrosion, but also had the active dissolution of the passive film. Therefore, the anti-corrosion performance of Fe-based amorphous/nanocrystalline coating under alkaline conditions was not as good as neutral and acidic corrosive medium.Compared with crystalline alloys and stainless steels of the same composition, amorphous alloys have excellent wear and corrosion resistance, so they are ideal coating materials for applications in marine and industrial fields [3,4]. For example, in the power industry, boiler pipes, steam turbine rotating shafts, blades, valve elbows, and other key components are subject to severe wear, corrosion, or erosion, which poses safety hazards to the long-term operation of power station equipment [5]. The application of amorphous coatings to protect the surface of these components is an effective technical method to solve those problems. Amorphous coatings also have huge application prospects for protection of steel facilities (such as television towers, bridges, road facilities, floodgates, microwave towers, high-voltage transmission towers, underground cable supports, and even transportation and underground storage of nuclear waste) from long-term exposure to harsh outdoor environments [6]. Among those amorphous alloy materials, Fe-based amorphous alloys are the most attractive due to their unique properties including high hardness, superior corrosion and wear resistance, and relatively low cost [7][8][9]. They can be successfully coated on steel substrate by thermal spray technology [10][11][12][13][14], where the amorphous structure is retained due to sufficiently rapid cooling that prevents long-range diffusion and crystallization. These advantages have demonstrated an enhanced comprehensive performance on steel surfaces in industrial applications, such as a better corrosion resistance than electroplated Cr and stainless steel in NaCl solution [15,16].Many scholars have researched the corrosion behavior of amorphous coatings [17][18][19][20][21][22][23][24][25][26]. ...