A novel approach for the synthesis of 4-aminoquinazolines has been developed via rhodium(Ⅲ)-catalyzed[4 + 2]annulation of N-arylbenzamidines with 1,4,2-dioxazol-5-ones.This reaction features excellent regioselectivity,broad substrate scope and high step economy,which would provide the reference for the construction of the fused 4-aminoquinazolines with biologically and pharmacologically active compounds.