Selective-reductive leaching of manganese from low-grade manganese ore using tannic acid as a reductant in acidic media was demonstrated by XRD, SEM-EDX characterization, and batch leaching studies at room temperature. The pH change in the liquid phase before and after leaching revealed that selectivity of manganese over iron was due to the hydrolysis of iron. The acidity in the liquid phase during leaching was dictated by two mechanisms: proton-consuming reaction (manganese oxide reduction by tannic acid) and proton-producing reaction (ferric ion reduction by tannic acid to produce ferrous ion). Based on the leaching studies, the more prevalent reaction between these two was determined by initial leaching conditions: tannic acid concentration, sulfuric acid concentration, liquid-solid ratio, temperatures, and agitation time. Kinetic studies revealed that maximum recovery was attained within 6-h agitation, which indicated a product layer diffusion process.