Based on the structure of lead compound N-(m-fluoro-benzyl)-6-amino-coumarin, a series of novel N-acyl-N-(m-fluoro-benzyl)-6-amino-coumarins were designed and synthesized through the principle of bioactive substructure combination. Their structures were characterized by 1 H NMR, ESI-MS and elemental analysis. N-trifluoroacetyl substituted compound d5 was further confirmed by X-ray single crystal diffraction. The herbicidal activities of synthesized compounds were evaluated as well. The results indicated that compounds substituted respectively by N-chloracetyl, N-bromoacetyl, N-trifluoroacetyl and N-(2,4-dichlorophenoxyacetyl) compounds d2, d3, d5 and d17 exhibited marked inhibition against the roots and stems of Amaranthus retroflexus with inhibitory rates above 75% at 100 mg/L, more active than acetochlor EC. In post-emergence treatment experiment, compounds d3 and d17 substituted respectively by N-bromoacetyl and N-(2,4-dichlorophenoxyacetyl) showed more than 76% inhibition against A. retroflexus and other dicotyledons at 1500 g/ha in greenhouse. Compound d17 is safe to monocotyledonous crops wheat, corn and rice at 1500 g a.i./hm 2 .