Abstract: A high performance liquid chromatography-tandem mass spectrometry method(HPLC-MS/MS)was established to detect α-solanine and α-chaconine in potato and potato powder samples simultaneously. The samples were extracted with 10% acetic acid aqueous solution for 3 min,and potato powder samples were purified with Bond Elut C18 SPE column. The extraction was analysed by HPLC-MS/MS with C18 chromatographic column. The results showed that correlation coefficients were 0.9998 for α-solanine and 0.9997 for α-chaconine ranged from 0.01 μg/mL to 1.00 μg/mL. The recoveries of spiked potato and potato powder samples were 90%~110% with the relative standard deviation(RSD)from 1.6% to 5.0% in low,medium and high concentration. The limit of quantity(LOQ)of α-solanine and α-chaconine in potato samples was 0.80 μg/kg and 0.42 μg/kg respectively(S/N=10),and the LOQ in potato powder samples was 25 μg/kg and 14 μg/kg respectively(S/N=10). The method was simple and rapid with high sensitivity and repeatability,and it was suitable for simultaneous detection of α-solanine and α-chaconine in potatoes and potato powder samples.