The invention provides an aziridine derivative and a preparation method and application thereof. In the preparation process, sultam is adopted as a substrate, phosphonium salt is adopted as a catalyst, cycloaddition is carried out, and the target compound is obtained. The chiral phosphonium salt phase transfer catalyst derived from natural amino acid is adopted as the catalyst, and the catalyst ischeap, easy to obtain and stable for water and oxygen. The simple and efficient new preparation method is provided for construction of polysubstitution ring fused and polysubstitution volute chiral aziridine derivatives. The constructed chiral aziridine derivative is a kind of important heterocyclic ring molecules with potential biological activity, and meanwhile the obtained target product has high stereoselectivity.