A method for qualitative analysis of constituents in Panax notoginseng by UPLC-LTQ-Orbitrap mass spectrometry was established.  Based on the high-resolution mass information, MS/MS fragmentation behaviors and chemical components from literatures, 43 compounds were identified or tentatively characterized.  New type saponin aglycone, combined with malonyl-substituted and acetyl-substituted saponins were discovered and plausibly identified in this study.  This work could be helpful for the quality control and further phytochemical studies of Panax notoginseng, and provided a good example for the analysis of chemical constituents in traditional Chinese medicine.