Four new flavonol glycosides (1-4), polygalins D-G, together with 12 known flavonoids (5-16) were isolated from the aerial parts of Polygala sibirica L. The chemical structures of these compounds were characterised by NMR and ESI-MS spectroscopic data and acid hydrolysis results. This report is a continuous research work on the systematic chemical investigations of plants of the genus Polygala in our laboratory.