A series of novel N,N'‐disubstituted‐1,2,3,4‐tetrahydroquinoxalines were designed and synthesized by cyclization and acylation. The structures of all the novel compounds were confirmed by IR, 1H NMR, 13C NMR, and high‐resolution mass spectrometry. The configuration of 4d was determined by X‐ray diffraction. The preliminary biological tests showed that all the products could protect maize against the injury caused by acetochlor to some extent.