ABSTRACT Here, a hydrometallurgical process was proposed to separate nickel (Ni) and iron (Fe) from ferronickel. The effects of different factors, namely hydrothermal temperature, initial Fe2+ concentration, and Ni2+ concentration, on the hematite precipitation process, were detail investigated. Ferronickel powders were leached using a 120 g/L H2SO4 solution at 85 °C for 8 h. The final pH of the leaching solution was controlled at 3.0−4.5, and the Fe2+ concentration was maintained at 50−60 g/L. Copper from the ferronickel powder was first leached in the early stage of the leaching process, and then it was reduced by an excess of ferronickel powder, leading to its enrichment in the leaching residue. Approximately 50 g/L of Fe ions was successfully removed and precipitated as hematite containing 60% Fe, 0.3% Ni, and 1.5% S during hydrothermal precipitation at 200 °C for 3 h. Through evaporation crystallization at 90 °C for 8 h, large particles of nickel sulfate hexahydrate (NiSO4·6H2O) containing 19.4% Ni, 0.074% Fe, and 10.69% S were obtained. Moreover, through freezing crystallization at −8 °C for 1 h, smaller particles of NiSO4·6H2O product containing 20.3% Ni, 0.014% Fe, and 11.13% S were synthesised.