Abstract: Precursors of chromium oxide (p-Cr₂O₃) were prepared by reducing hexavalent chromium in the presence of sodium carbonate solution under hydrothermal conditions. Methanal was used as the reductant, and carbon dioxide was the acidulating agent. The influences of reaction temperature, initial pressure of carbon dioxide, isothermal time and methanal coefficient on Cr(VI) reduction were investigated. Experimental results showed that Cr(VI) was reduced to Cr(III) with a yield of 99%. Chemical titration, thermogravimetry (TG), X-ray diffraction (XRD) analysis, and scanning electron microscopy (SEM) were used to characterize the p-Cr₂O₃ and Cr₂O₃. The series of p-Cr₂O₃ were found to be multiphase even if they presented different colors, from gray green to lavender. After these p-Cr₂O₃ samples were calcined, the product of rhombohedral Cr₂O₃ with a purity of 99.5wt% was obtained.