Manganese sulfate residues would be generated when pyrolusite ore is used for manganese sulfate production. Two kinds of residues derived from different pyrolusite processes were characterized using XRF, XRD and SEM, including manganese sulfate residue from pyrolusite and pyrite method (MSR-PP) and manganese sulfate residue from flue-gas desulfurization method (MSR-FD). The concentrations of water-soluble metals from MSR-PP and MSR-FD were investigated. It shows that water-soluble manganese concentrations in MSR-PP and MSR-FD were as high as 1850 and 2170 mg/L, respectively, which might be a manganese contaminant source. Extraction procedure for leaching toxicity experiments shows that MSR-PP should be identified as hazardous waste for its extraction metal of nickel achieved 5.79 mg/L.