Abstract An iron‐catalyzed approach was described for the synthesis of pyrrolo[2,1‐ a ]isoquinolines via oxidative [3+2] cycloaddition‐aromatization reaction using “aqueous tert ‐butyl hydroperoxide (T‐HYDRO)” as an oxidant. The cascade reaction proceeds well with a broad substrate scope at room temperature in a short time and generates “desired products in moderate to high yields.”