We report here a selective C6‐nitration of benzothiazolones in the presence of iron nitrate as nitro source. A series of novel 6‐nitrobenzothiazolin‐2‐one derivatives were prepared with moderate to excellent yields at room temperature. The method shows good regioselectivity, broad substrate scope and excellent compatibility with functional groups. Further transformations were performed for the reduction of nitro groups, amination of carbonyl groups and alkylation of amine at the 3‐position in the product.