Polymeric tannins, extracted from grape berries (Gamay variety), were fractionated according to their mean degree of polymerisation (mDP) on a styrene-divinylbenzene phase eluted with a gradient of methanol:chloroform. Increasing the percentage of methanol led to the solubilisation of higher molecular weight tannins. The mean mDP of each collected fraction was determined by acid-catalysed degradation in the presence of a nucleophilic reagent. The fractionation method produced a linear gradient of mDP varying between 1.84 and 19.34. The fractions were partially characterised by matrix assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF/MS). The spectra showed a complex mixture of proanthocyanidins and galloylated proanthocyanidins up to 4000 amu.