Amorphous alloy is a new type of material that exhibits exceptional properties or combinations of properties that are often not achievable in conventional crystalline materials. Fe-based amorphous alloys has attracted significant attention over the last few decades because of their low cost and enhanced mechanical performance. However, they are more suitable for the industrial application of coatings due to the fatal disadvantages of poor toughness. High velocity oxygen-fuel (HVOF) spraying is a good way to make amorphous alloy coatings (AMCs), for the individual droplets are cooled at a rate of around 10⁷ K/s which is much higher than the critical cooling rate of the amorphous alloys during the thermal spraying. Fe-based AMCs obtained by using the HVOF spray method are important materials for industrial applications because of high glass-forming ability and exceptional performances, such as excellent corrosion resistance, high hardness, and superior wear resistance. In this work, FeCrMoMnWBCSi AMCs were prepared by HVOF thermal spray. The microstructure and amorphous characteristics of AMCs were characterized by SEM and XRD. Electrochemical corrosion behavior of AMCs was investigated in different concentration of NaCl and H₂SO₄ solutions compared with that of 304 stainless steel and ND steel. The surface film of materials after immersed in two solutions was analysed by XPS. The results indicated that HVOF thermal spraying Fe-based AMCs presented dense layered structure, high amorphous phase content and low porosity. The composite structure of AMCs was formed with some nanocrystallite phases embedded in the amorphous matrix. AMCs exhibited better resistance to pitting corrosion and relatively low uniform corrosion resistance due to the porosity, while the pitting potential of 304 stainless steel was sensitive to NaCl concentration. XPS results revealed that the presence of Cr, Mo and W oxides in the passive film of AMCs may result in the better corrosion resistance. The enrichment of Mo⁴⁺ oxides on the surface favored the formation of a more stable and protective layer which could be assumed to be responsible for the observed high stability of passive film. The diminishing or avording pores may be beneficial to further improve the pitting corrosion resistance of AMCs in NaCl solution. In all cases, AMCs showed better resistance to H₂SO₄ solutions corrosion due to the high stability of passive film. 304 stainless steel and ND steel presented stable passivation behavior only in high concentration of H₂SO₄ solution. In the lower concentration solution of H₂SO₄, the amorphous structure of the thinner coatings could facilitate the formation of thicker passivation film and lead to the higher corrosion resistance. The corrosion resistance of AMCs in H₂SO₄ solution could be enhanced significantly by formation of high amorphous phase.