The first phytochemical investigation on D. grandifoliolata yielded twenty-four alkaloids, including four new ones, N-butylacetamide magnococline (1), fumariflorine methyl ester (6), (R)-corydalisol-2β-N-oxide (9), and (R)-coryximine-2α-N-oxide (10). Among them, compound 1 was an N-butylacetamide-substituted benzylisoquinoline alkaloid. Compounds 9 and 10 were N-oxides of benzylisoquinoline alkaloids. The structures of the new alkaloids were determined through comprehensive spectroscopic analysis and ECD calculations.