The aim of this work was to determine the structural characteristics of the condensed tannins isolated from the aqueous extract of black spruce (Picea mariana Mill) bark. This is the first report on the structural characterization of condensed tannins from black spruce bark. The condensed tannins from the hot water extract prepared from Picea mariana bark were isolated by column chromatography on Sephadex LH-20 media. In this study, UV-visible and ¹³C-NMR spectroscopic techniques, along with pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and liquid chromatogramphy analyses were applied to determine the structural characteristics of black spruce bark tannins. We have confirmed for the first time the presence of methoxylated B-rings in the flavanol units of condensed tannins from black spruce bark, which could be regarded as further contribution to the chemotaxonomy of the genus Picea. The methoxylation of Norway spruce bark condensed tannins have been demonstrated previously.