(±)-Decumicorine A ( 1 ) and (±)- epi -decumicorine A ( 2 ), two pairs of enantiomeric isoquinoline alkaloids featuring a novel phenylpropanoid-conjugated protoberberine skeleton, were isolated and purifi ed from the rhizomes of Corydalis decumbens . The separation of (±)- 1 and (±)- 2 was achieved by chiral HPLC to produce four optically pure enantiomers. The structures and absolute confi gurations of compounds (−)- 1 , (+)- 1 , (−)- 2 , and (+)- 2 were elucidated by spectroscopic analysis, ECD calculations, and X-ray crystallographic analyses. The two racemates were generated from a Diels-Alder [4 + 2] cycloaddition between jatrorrhizine and ferulic acid in the proposed biosynthetic pathways, which were fully verifi ed by a biomimetic synthesis. Moreover, compound (+)- 1 exhibited an antiviral entry eff ect on SARS-CoV-2 pseudovirus by blocking spike binding to the ACE2 receptor on HEK-293T-ACE2 h host cells.