With the combination of high performance liquid chromatography-electrospray ionization mass spectrometry (HPLC/ESI-MS) and electron impact mass spectrometry (EI-MS), two steroidal saponins, one compound containing three glycosyls and tigogenin and the other one containing three glycosyls and diosgenin, from the bulbs of Lilium brownii var. calchesteri in China have been screened. In the method, on-line HPLC/ESI-MS allows us to obtain rapidly useful information about the molecular weight and the glycosyl chain of glycoside without the necessity of isolating individual compounds, but little information about steroidal sapogenins. Just with 1 mg to 2 mg of pure sample, off-line EI-MS allows us to acquire useful information about a steroidal sapogenin of saponins, but it is difficult to obtain the molecular ion peak. The combination of HPLC/ESI-MS and EI-MS is well suitable for rapidly screening steroidal saponins from plants.