Traditional Chinese Medicine (TCM) based on natural products is one important part of the Chinese civilization. Owing to the complexity of the composition, the study on medical effective components and curative effects are very difficult. Fuzi (Radix Aconiti Lateralis Praeparata) has been widely used for cardiotonic and analgesics in China,however, the component-aconitine in which is very toxic and may cause some side-effect.This paper reported the application of electrospray iohization mass spectrometric(ESIMS)technique on study of the compound prescriptions containing fuzi, Renshensini concoction and Baweidihuang concoction, to explore the mechanism of synergy between fuzi and other herbs. From chemical point of view, the detoxification mechanism can be attributed to the hydrolysis of the solubility of toxic diester-alkaloids from concoctions of fuzi. Radix Glycyrrhizae Praeparata, Rhizoma Zingiberis, Radix Ginsengp promote the hydrolysis to produce the less toxic monoester-alkaloids and Fructus Corni reduce the solubility of hypa-conitine from fuzi. However pinellia fritillary and bletilla were forbidden to use with fuzi,because they suppress the hydrolysis of fuzi in the solution. This work applied electrospray ionization mass spectrometry, tandem mass spectrometry (MSn) , high performance liquid chromatography (HPLC) techniques to study the reactions (including hydrolysis and ester-exchange reaction etc. ) occurred during the decoction and the concoction process via the gas phase ion chemical reactions and discuss the conditions to the reactions. On the other hand, the fragmentation mechanism of aconitine alkaloids in mass spectrometry was studied as well.