Nano-single-unit-cell hierarchical Fe-ZSM-5 (designated NSUCH Fe-ZSM-5) was successfully synthesized and characterized by X-ray diffraction, scanning electron microscope, transmission electron micrographs, inductive coupled plasma emission spectrometer, and X-ray photoelectron spectroscopy techniques. NSUCH Fe-ZSM-5 exhibits great lamellar crystal structure and Fe species are present in the form of crystalline gamma-Fe2O3. Most of the Fe species got into mesoporous zeolite channels, presenting in a well-dispersed state. The adsorbed oxygen on an external surface is a benefit for the NH3-NO selective catalytic reduction reaction. The catalytic behaviors for removal of nitrogen oxides reveal that NSUCH Fe-ZSM-5 displays better activity than conventional Fe-ZSM-5 during the temperatures of 250-400 degrees C.