<p>The global alumina industry generates approximately 170 million tons of red mud annually, whose strong alkalinity and high iron content pose not only persistent environmental pressures but also significant challenges for resource recovery. Conventional disposal methods struggle to balance economic viability with ecological benefits, underscoring the urgent need for innovative valorization technologies. This work explores the feasibility of utilizing red mud by investigating the electrochemical reduction behavior of iron phases under highly alkaline conditions. The occurrence state and electrochemical behavior of iron phases in red mud within a highly alkaline electrolyte were systematically studied. Results show that minor dissolution of iron phases into the electrolyte markedly enhances the adsorption of iron oxides from red mud particles onto the cathode surface, thereby establishing favorable interfacial conditions for electroreduction. Cyclic voltammetry reveals that iron reduction in red mud proceeds <i>via</i> a two-step consecutive diffusion-controlled mechanism (Fe³⁺ → Fe²⁺ → Fe⁰). Furthermore, increasing temperature and NaOH concentration significantly improves iron phase solubility and strengthens oxide–electrode adsorption interactions. Based on these insights, optimization of key parameters particularly current density and electrolytic potential demonstrates that lower current densities combined with moderately negative potentials yield high-purity electrolytic iron (&gt; 97 pct) with sustained high current efficiency (&gt; 84 pct). Preliminary techno-economic analysis suggests that the proposed process can be seamlessly integrated into the Bayer process, substantially mitigating red mud’s environmental toxicity while generating valuable iron by-products. Overall, this work establishes a theoretical foundation and practical pathway for low-carbon, efficient iron recovery and resource utilization from red mud.</p>