<p>Metallic glasses are widely investigated for corrosion due to their compositional homogeneity. To mitigate the deficiency of low plasticity in metallic glasses and expand their application scenarios, this study designed the novel Fe₅₂Ni₅Nb₅Cr₁₆Mo₅B₁₂Si₅ metallic glass coatings. The systematic investigation into crack and pore formation established a direct correlation between the HVAF process parameters, key coating quality indicators (compactness and amorphous phase content), and corrosion resistance, leading to the successful fabrication of dense coatings free of macroscale defects. During corrosion, the passive film formation follows a sequential process. First, Si oxidation establishes a primary film matrix. Then, the subsequent incorporation and accumulation of Cr₂O₃ within this matrix plays a critical role in densifying the passive film. This densification process is key to improving the film’s barrier property against Cl⁻. Conversely, localized pitting primarily results from the reduction of Mo⁶⁺ to Mo⁴⁺, which compromises the film’s local stability.</p>