Objective To establish a method for determination alpha-solanine in potatoes by liquid chromatography-tamdem quadrupole mass spectrometry. Methods The potato samples were extracted using the mixed solution of acidity water and organic solvent by accelerated solvent extraction . After the purification by MCX solid phase extraction, the eluent was dried-up with nitrogen. The analytes were dissolved by the mobile phase and separated by hydrophilic interaction chromatography and determined using multi-reaction monitoring mode. The conditions of the pretreatment solution and liquid chromatography and matrix effect were optioned Results The limits of quantification and detection were 0.5 μg/kg and 1.6 μg/kg. The linear range of standard curve were from 0.1 μg/L to 100 μg/L. The relative standard deviations of detection were at 3.41 %～7.56%, the spiked sample recoveries of analytes were at 82.8 %～99.0%. Conclusion The simplicity, high efficiency of accelerated solvent extraction and the separation effect of hydrophilic interaction chromatography and the sensitivity, accuracy of tamdem quadrupole mass spectrometry can meet the needs of risk monitoring and poisoning analysis.