Multiple mass spectra (MS1 to MS6) of 55 phenylalkylamine derivatives were recorded with ion-trap mass spectrometry employing electrospray (ESI) and atmospheric pressure chemical ionization (APCI). Fragmentation patterns were studied in detail and a generally applicable scheme was established for elucidation of the structures of phenylalkylamine derivatives. HPLC combined with ion-trap multiple mass spectrometry was used to identify the structure of reaction by-products in ecstasy samples from the "black” market. Low nanogram amounts were sufficient for on-line HPLC-MS n structure elucidation of unknown