Hydrocarbon fuels have caused significant environmental damage, leading to a search for renewable alternatives like hydrogen. The water-gas shift reaction (WGSR) is a key process in hydrogen production, especially in ammonia synthesis. Typically, WGSR occurs in two stages: low-temperature (LT-WGSR) at 180–250 °C and high-temperature (HT-WGSR) at 310–450 °C. Traditional HT-WGSR catalysts use Fe–Cr, but the presence of carcinogenic hexavalent chromium (Cr6+) poses environmental risks, necessitating safer alternatives. This study explores the replacement of chromium with aluminum (Al) and cerium (Ce) in Fe-based catalysts, synthesized via mechanochemical methods. Characterization revealed that Fe–Ce catalysts (85:15 ratio) exhibited superior thermal stability. Additionally, varying nickel (Ni) contents were tested to improve activity, with 10% Ni offering the best performance despite some methane by-products. The study also examined the impact of reduction and calcination temperatures, GHSV, and steam/gas ratios on the catalyst's efficiency.