The microstructure and the chemistry distribution of AlNiCo 9 samples were characterized by the X-ray diffraction, magnetic force microscope, field emission scanning electron microscopy and transmission electron microscope. An interface of a high Al content was formed near the FeCo-rich phases with a size of about 30 nm. S elements mainly combined with Ti to form titanium sulfide bars with the length between 70-150 μm, while S elements was not confirmed in the nanostructured FeCo-rich phase and AlNi-rich phase. Si and Nb preferably existed in the NiAl-rich phase, and a higher content Nb near the Cu precipitate boundary was observed. Moreover, the magnetic domain structure of AlNiCo 9 was also studied.