The molecular formula C90H68O36 gleaned from ()-HRESIMS and C NMR carbon counts identified 3 as a hexamer with 3A+2B IFLs. The close resemblance of the 1 H and C NMR resonances of units II/IV and III/V, as well as their congruence with reported data of the major tetramer from peanuts, peanut procyanidin E, suggested this tetramer plus an additional A-type dimer as building blocks of 3. Its 1 H NMR spectrum revealed three AX-type doublet pairs (H 4.13 and 4.47, J = 3.4 Hz; H 4.17 and 4.38, J = 3.6 Hz; and H 4.12 and 4.23, J = 3.6 Hz), which corroborated the presence of three doubly linked A-type motifs. Similarly, two B-type single bond linkages were assigned by the observed two sets of three coupled methines resonating as broad singlets at H 5.27, 4.04, and 4.74 as well as H 5.42, 3.89, and 4.78.