<p>The sulfion oxidation reaction (SOR) has enormous potential in replacing slow kinetic oxygen evolution reactions and treating sulfur-containing wastewater. However, the sulfur aggregation generated by SOR will lead to a decline in SOR activity. Herein, an electrospinning-carbonization-vulcanization technique is introduced to fabricate Mo-NiS₂-co-embedded carbon nanofibers (Mo-NiS₂/CNFs). The integration of molybdenum promotes sulfophobicity of Mo-NiS₂/CNFs, and can thus effectively prevent its activity from being deactivated by sulfur deposition on the electrode surface during SOR, thereby improving catalytic activity and long-term stability. In particular, Mo-NiS₂/CNFs showed a distinguished durability at 100 mA cm⁻² at least 100 h. <i>In-situ</i> Raman spectra tracked the evolution and oxidation conversion of S²⁻ to short-chain polysulfides (S₂²⁻–S₄²⁻), ultimately to value-added S₈. Density functional theory calculations unveiled that the introduction of Mo efficiently regulated the <i>d</i>-band center of NiS₂, reduced the energy barrier in the rate-determining step from S₂²⁻ to S₃²⁻ and the Gibbs free energy of H* adsorption, and thereby significantly promoted SOR and hydrogen evolution reaction (HER). Mo-NiS₂/CNFs-based anion exchange membrane water electrolyzer for HER and SOR achieved a current density of 500 mA cm⁻² at 1.78 V for continuous H₂ and S₈ productions. Such a coupling system performed an ultra-low power consumption of 2.127 kW h m⁻³ H₂ at 500 mA cm⁻², showing an energy-saving hydrogen production and high desulfurization ability for environmental protection and remediation.</p>