LC/(+)ESI/MS(3) was used to determine aconitine, mesaconitine, and hypaconitine as target markers in crude methanol extracts of (i) the raw lateral roots of Aconitum carmichaeli, (ii) roots treated by three different refining processes, and (iii) eight generally available traditional Chinese medicine (TCM) preparations containing fuzi (treated lateral roots of A. carmichaeli). The optimal ionization behavior resulted when using electrospray ionization (ESI) in positive-ion mode with 0.005% TFA as an additive in the mobile phase. The consecutive reaction monitoring (CRM) mode provided additional improvements in selectivity, which was exploited to minimize the noise and interference problems. Employing this approach, aconitine and mesaconitine were found to decompose readily during the refining processes, but hypaconitine remains present at the same content, presumably because of its characteristic chemical structure. Thus, treated and untreated fuzi samples can be distinguished by monitoring the ratio of aconitine and mesaconitine to hypaconitine. The limits of detection (LODs) for these three markers were 0.05, 0.08, and 0.03 ng/ml. The linearity range for the three marker compounds was 0.1-1,000 ng/ml. The analysis time was 12 min per sample.