A solid-phase extraction method was applied for the identification of a series of unconventional crown (macrocyclic) B-type proanthocyanidin tetramers (m/z 1169.2557, 1185.2507, 1201.2456, and 1217.2405) and pentamers (m/z 1457.3191, 1473.3140, 1489.3090, 1505.3039, and 1521.2988) containing (epi)catechins only (procyanidins) or (epi)catechins and (epi)gallocatechins (prodelphinidins). These compounds were identified in red wine by high-performance liquid chromatography–high-resolution mass spectrometry coupled with online hydrogen/deuterium exchange (HDX) after purification with a C18 solid-phase extraction phase from the original wine sample. The number and type of monomer units present in each procyanidin and prodelphinidin are discussed on the basis of the experimental measured masses, their retention time distribution among observed isomers, tandem mass spectrometry fragmentations, and the HDX-induced shift of the theoretical monoisotopic mass. The elution in reverse-phase high-performance liquid chromatography shifted to lower retention times when the ratio of (epi)gallocatechin units in these molecules increased with respect to the content of (epi)catechin units, as a consequence of the increase of polarity.Read less <