After the process of carbonization and fine grinding, the biomass of higher C and lower S elements and ash contained in agricultural wastes, when mixed with pulverized coal, are to be injected into blast furnace for combustion, which can effectively utilize renewable energy, reduce CO2 emission of iron-making industry, improve cast iron quality, and significantly improve the combustion rate of pulverized coal. Therefore, a characterization analysis has been made of the pyrolysis products of corn straw and peanut hull, and based on the differential thermal analysis, a research has been carried out on the effects of different mixing ratios of the two biomass charcoal on the combustion performance of pulverized coal. SEM and BET test results show that the corn straw charcoal and peanut shell are characterized with a loose structure, a large specific surface area and a low value of sulfur and ash content, which helps to significantly increase the contact area between sample and oxygen. The thermogravimetric test results show that the combustion performance of the mixture of biochar and pulverized coal is the best with a mass ratio of 3:7, with its ignition point obviously reduced, the combustion process stabilized and the combustion rate significantly increased.