$De-NO_x$ transition metals(Cu, Co)/ZSM-5 catalyst was made by mechanical alloying method, and their microstructures and repeated usage-properties were investigated by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The conversions ability of NO in the catalyst was measured. A part of ZSM-5 in CO/ZSM-5 composite powders was amorphous and the amorphous phase became less stable with increasing Co content. Conversion ability of NO in 10Cu/ZSM-5 powders decreased from 89% to 12% and that in 10Co/ZSM-5 decreased from 22% to 17% by 7 times conversion tests.