In the present study, a qualitative analysis of proanthocyanidins (PAs) from an aqueous-methanolic extract of Salix daphnoides VILL. bark is described. Procyanidin B1 (1), B2 (2), B3 (3), B4 (4), C1 (5), epicatechin-(48)-epicatechin-(48)-catechin (6) and epicatechin-(48)-epicatechin-(48)-epicatechin-(48)-catechin (7) have been isolated by a combination of different chromatographic separations on Sephadex((R)) LH-20-, MCI (R)-, Diol-and RP-18-phases. Mass spectrometry, 1D- and 2D-NMR, circular dichroism and polarimetry were used for their structure elucidation and verification by comparison with the literature. Additionally, two fractions of very polar flavan-3-ols were compared: regular polymeric PAs received at the very end of the Sephadex((R)) LH-20 chromatography showing no mobility on silica TLC and unusual PAs with the same R-F-value but already eluting together with flavonoids in the Sephadex((R)) LH-20 system. These unusual PAs were subsequently enriched by centrifugal partition chromatography (CPC). C-13-NMR, polarimetry, thiolysis, acid hydrolysis and phloroglucinol degradation were used to characterize both fractions. Differences in the composition of different flavan-3-ol units and the middle chain length were observed.