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Fe-based amorphous alloys are an eco-friendly alternative to Ni- and Co-based amorphous alloys, which are not sustainable. Herein, amorphous Fe–P alloys were electrodeposited from an eco-friendly aqueous electrolyte. The influence of bath temperature on the electrochemical behaviour during Fe–P alloy deposition was investigated using linear-sweep voltammetry, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry. The morphology, P content and phase structure were characterized via scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction and differential scanning calorimetry. The electrochemical corrosion behaviour in 3.5 wt% NaCl solution was studied using potentiodynamic polarization curves and EIS spectra. The results showed that an increase in bath temperature leads to a positive shift in the inductive co-deposition potential and increases the reaction rate. At bath temperatures of 20–60°C, the P content in deposits varied in the range of 17.07–21.13 wt% and the phase structure was amorphous. Although the amorphous alloys lacked crystalline defects, the P content had a marginal effect on the corrosion properties, whereas the surface morphology significantly influenced the corrosion properties. The amorphous Fe–P alloys fabricated in this study exhibit superior corrosion properties to almost all electrodeposited amorphous alloys reported in the literature, demonstrating their potential for corrosion protection. [ABSTRACT FROM AUTHOR]