First on-line HPTLC-MS methods on silica gel for proanthocyanidins up to decamers. Ionization suppression was solved by two pre-developments of HPTLC plates. Stability testing after development revealed a phenomenon of enhanced absorption. Free and galloylated B-type proanthocyanidins were identified in Japanese knotweed. HPTLC-MS methods enabled also identification of stilbenes and anthraquinones.