Mineral phase transformation (MPT) of hematite to magnetite by reduction roasting is a viable means of developing refractory iron ore resources. However, conventional coal-based reductants are prone to high carbon emissions and environmental pollution. Biomass, as a renewable green reductant, can make the MPT process more environmentally friendly while reducing the environmental impact associated with processing agricultural waste. This study systematically explored the feasibility of waste corn straw as a green reductant for hematite. Under the conditions of 8 min, 700 °C, a mass ratio of corn straw to hematite of 1:4, and a N2 flow rate of 300 mL/min, the best beneficiation indexes were achieved, with an iron grade of 69.82% and an iron recovery of 93.95%. During the MPT process, hematite was reduced under the action of corn straw, and the new magnetite particles were loose and porous, showing an acicular crystal structure. Meanwhile, the corn straw was converted into porous biochar.