Abstract The electrochemical reduction of iron oxides in highly alkaline media (pH ≥14) offers a promising low-temperature, low-carbon pathway for sustainable iron production. However, the harsh conditions limit the use of conventional reference electrodes (RE), while accurate interpretation of electrochemical data depends critically on RE’s reliability. Here, platinum wire is evaluated as a quasi-reference electrode (QRE) during the electrochemical reduction of hematite (Fe2O3) in 10M NaOH at 75°C. Cyclic and linear sweep voltammetry reveal a Fe2O3 reduction peak near -1.1V vs Pt QRE, followed by hydrogen evolution around -1.25V. Chrono-potentiometry demonstrates sustained iron deposition for up to 10h with Faradaic efficiencies of 50–60%, confirming the feasibility of alkaline electrochemical ironmaking. X-ray diffraction and SEM-EDX analysis confirm phase-pure metallic α-Fe formation with a dendritic morphology. The Pt QRE performed reliably under low current operations but showed significant drift at higher currents as hydrogen evolution drives equilibration of the Pt surface with the H2/H2O couple, resulting pseudo-reversible hydrogen electrode behavior. Auxiliary channel measurements of WE-RE, WE-CE, and CE-RE couples confirmed the RE as the source for potential drifting. Complementary measurements using a Hg/HgO RE validated with Pt QRE results within a 70-100 mV shift at low currents while delineating their limitations clearly.