The fingerprints of Aconitum L. plants, Radix Aconiti (RA), Radix Aconiti Singularis (RAS), Radix Aconiti Kusnezoffii (RAK), Radix Aconiti Lateralis Preparata (RALP) and Radix Aconiti Brachypodi (RAB), were established by ultra-high performance liquid chromatography (UPLC) and the metabolism of Aconitum L plants on Escherichia colt (E. coil) were studied by microcalorimetry. The spectrum-effect relationships between UPLC fingerprints and bacterial metabolism were investigated using canonical correlation analysis (CCA). Because of their inherent differences of chemical compositions, the main actives of bacterial metabolism were different among five Aconitum L plants. The potency bioactivity sequence of the tested five Aconitum L products on E. coil was obtained that were RAB > RALP > RAK > RAS > RA. This work establishes a universal model of the combination of UPLC and microcalorimetry to study the spectrum-effect relationships of Aconitum L plants, which offers some references for detecting principle components of traditional Chinese medicine on bioactivity. (C) 2013 Elsevier B.V. All rights reserved.