The complexity of natural products always leads to the co-elution of interfering compounds with bioactive compounds, which then has a detrimental effect on structural elucidation. Here, a new method, based on selective solid phase extraction combined with 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) spiking and high performance liquid chromatography-diode array detector-quadrupole time-of-flight tandem mass spectrometry (HPLC-DAD-QTOF-MS/MS), is described for sensitive screening, selective extraction and identification of polyphenolic antioxidants in Polygonatum odoratum. First, 25 polyphenolic antioxidants (1-25) were screened by DPPH spiking with HPLC. Second, polydopamine coated Fe3O4 microspheres (Fe3O4@PDA) were prepared to selectively extract target antioxidants with extraction efficiency from 55% to 100% when the amount of Fe3O4@PDA, extraction time, desorption solvent and time were 10mg, 20 min, acetonitrile, and 5 min. Third, 25 antioxidants (10 cinnamides and 15 homoisoflavanones) were identified by HPLC-DAD-QTOF-MS/MS. Furthermore, the DPPH scavenging activities of purified compounds (IC50, 1.6-32.8 μg/mL) validated the method. Among the identified antioxidants, four of them (12, 13, 18 and 19) were new compounds, four of them (2, 4, 8 and 14) were first obtained from family Liliaceae, five of them (1, 3, 5, 7 and 9) were first reported in genus Polygonatum, while one compound (24) was first identified in this species. The results indicated that the proposed method was an efficient and sensitive approach to explore polyphenolic antioxidants from complex natural products.