Abstract: In this paper, an efficient method for synthesizing (Z)-2-((hydroxyimino)(phenyl)methyl)isoindoline-1,3-diones and isolating of Z-aldoximes has been developed. In the presence of DBU, the (Z)-2-((hydroxyimino)(phenyl)methyl)isoindoline-1,3-dione skeletons were constructed via the halogen-bonding-directed acylimide functionalization of the C—H bond of aldehyde oximes. The products were prepared with 70%–85% yields and their structures were validated by ¹H NMR, ¹³C NMR, IR, and high-resolution mass spectrometry. Solvent-stabilized Z-aldoximes were also obtained. This methodology features transition-metal-catalyst free, readily available substrates, mild reaction conditions, simple operation, and high chemoselectivity.