Abstract: Conventional blast-furnace ironmaking relies significantly on coke and other carbonaceous reductants and is characterized by a long process chain, high energy consumption, and substantial carbon-emission intensity. To support low-carbon transition in the iron and steel industry, high-temperature electrolytic reduction technologies, which replace carbonaceous reductants with electrons, have garnered increasing attention. This review systematically examines the fundamental principles, key influencing parameters, and industrial development of molten-oxide electrolysis (MOE), molten-salt electrolysis, and molten-salt electro-deoxidation—represented by the Fray–Farthing–Chen process (FFC) Cambridge process—for the production of metallic iron and ferroalloys. Recent advances in melt-structure regulation, electrode-material development, and related process optimizations are emphasized. The abovementioned three high-temperature electrolysis routes, which exhibit distinct industrialization pathways, are compared with conventional blast-furnace ironmaking in terms of process characteristics, carbon emissions, energy consumption, and production costs. MOE can directly produce liquid iron, making it more suitable for the production of primary liquid iron for the bulk steel industry. However, its commercialization is limited by the service life of inert anodes and refractory linings, continuous feeding and tapping, and high-temperature thermal management. Molten-salt electrolysis is more suitable for producing high-purity, fine, or morphology-controlled iron powders; however, its further development is limited by the dissolution and mass transfer of iron-bearing species, electrolyte stability, and downstream product purification. The FFC process is advantageous in the direct electro-deoxidation of solid oxides and the preparation of multicomponent alloy powders; currently, it is preferred in high-value metal and alloy-powder markets. This review further identifies the retention of high laboratory-scale current efficiencies and metallization degrees under large-scale, multielectrode, and long-term continuous operating conditions as a major unresolved challenge. Future studies should prioritize cross-scale performance validation, comprehensive process evaluation using actual iron ores and closed-loop salt-recycling systems, and differentiated commercialization strategies based on product form and technological maturity.