A series of Fe-based amorphous alloy wires with good formation ability, good flexibility, and a large specific surface area were prepared by the melt quenching method, which can be directly used as a self-supporting electrode for the oxygen evolution reaction (OER) of water electrolysis. By controlling the content of Mo, (Fe0.8Ni0.2)71Mo5P12C10B2 (Mo5), (Fe0.8Ni0.2)71Mo10P12C5B2 (Mo10) and (Fe0.8Ni0.2)71Mo15P10C2B2 (Mo15) alloy wires were prepared. It was found that Mo5 and Mo10 alloys still exhibit a fully amorphous structure, while the main body of Mo15 alloy comprises B2Fe3Ni3 and Mo6Ni6C phases. The electrochemical results showed that Mo15 alloy had the best intrinsic catalytic activity. The OER electrocatalytic performance of Mo15 was further improved by 1 h chemical etching after soaking in 0.5 M HNO3, which showed the overpotential was 239 mV and the Tafel slope was 40.6 mV/dec in 1 M KOH with a current density of 10 mA/cm2.