OBJECTIVE： To establish HPLC-quadrupole/electrostatic field orbitrap high resolution mass spectrometry for rapid determination of aconitine， mesaconitine， hypaconitine， benzoylaconitine， benzoylmesaconine and benzoylhypacoitine in rat plasma. METHODS： Internal standard lappaconitine was added into plasma sample， and methanol precipitated protein was used for pretreatment. HPLC-quadrupole/electrostatic field orbitrap high resolution mass spectrometry was adopted. HPLC condition was as follows as Sinochrom ODS-BP C18 column， mobile phase consisted of acetonitrile-1％ formic acid solution （50 ∶ 50，V/V）， the flow rate of 0.6 mL/min， sample size of 10 μL， column temperature of 25 ℃， automatic sampler temperature of 4 ℃. Mass spectrum scanning mode was full ion monitoring model， positive ion acquisition， mass charge ratios （m/z） of ion were 646.32（aconitine）， 632.30（mesaconitine），616.31（hypaconitine），604.31（benzoylaconitine），590.29 （benzoylmesaconine），574.30（benzoylhypacoitine）， 585.31 （internal standard）. Six male Wistar rats were collected and given single dose of total alkaloid extract of Aconitum carmichaeli （4 mg/kg）intragastrically. Blood samples were collected before medication （0 h） and 0.5， 0.75， 1.25， 1.5， 2， 4， 6， 8， 10， 24 h after medication. Plasma concentration was determined and pharmacokinetic parameters were calculated by using PK-Solver V2.0 software. RESULTS：The linear range of 6 kinds of aconitum alkaloids in plasma were 0.1-10 μg/L （r＞0.992）.  The limit of quantitation was 0.1 μg/L. Average recovery was higher than 75％， RSDs of intra-day and inter-day， matrix effects， stability test were all lower than 15％. The tmax of 6 kinds of aconite alkaloids  were about 1.2 h； t1/2 were about 10 h； cmax of monoestertype aconite alkaloids were higher than those of diester-type aconite alkaloids. CONCLUSIONS： Established HPLC-quadrupole/electrostatic field orbitrap high resolution mass spectrometry is accurate， sensitive， simple and rapid， and can be used for plasma concentration monitoring of 6 kinds of aconitum alkaloids.