The reaction between procyanidin dimer Ec-EcG (B2 3'-O-gallate) and malvidin 3-O-glucoside (Mv3glc) was studied in a model solution system at two different pH values, 2.0 and 3.8. Disappearance of both species was much faster at pH 3.8 than at pH 2.0. That of Mv3glc was increased in the presence of Ec-EcG, whereas that of Ec-EcG was the same in the presence or absence of the anthocyanin. Values of absorbance at 520 nm measured at pH 2.0 were correlated with the amount of residual Mv3glc. Those measured at pH 3.8 hardly changed during the incubation, but absorbance values at 420 and 620 nm as well as resistance to sulfite bleaching were much increased, confirming that Mv3glc was converted to other pigments. Anthocyanin-flavanol adducts were observed at both pH values, but their structures were different. At pH 2.0, cleavage of the procyanidin linkage followed by nucleophilic addition of flavanol or anthocyanin moieties led to (Ec)(n)-EcG and (Ec)(n)-Mv3glc, respectively. At pH 3.8, nucleophilic addition of Ec-EcG onto the anthocyanin yielded Mv3glc-(Ec-EcG).