Metal-binding sites in epigallocatechin gallate (egcg) were identified by measuring (1)H nuclear spin relaxation time T(1) under the coexistence of paramagnetic Mn(2+). The T(1) of the proton of gallate ring (D-ring) was shortened by the paramagnetic ion to a greater extent than the proton in gallocatechin ring (B-ring); the D-ring OH groups occupy the first coordination sphere around a metal ion to form a diolate chelate ring, while B-ring OH groups have a weak interaction with the metal ion. Comparison of changes in T(1) of egcg and epigallocatechin (egc) indicates that the gallate ring has a higher coordination capability than that of the gallocatechin ring so that the former plays a predominant role in the complex formation of egcg.