The micro structure of CFZ desulfurizer after desulfurization and regeneration in multi-cycle has been characterized by means of transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectrometry (XPS). The variation of the multi-cycle desulfurization and regeneration structure of desulfurzer has been analyzed as well. Therefore, with a view of micro structure, the effect of the variation of desulfurizer structure upon the performance of desulfurizer has been observed. It is demonstrated that the morphology was not changed greatly, the specific surface area decreased to 66.8%. However, the distributions of pores has been modified a great deal, and apparently, the larger and smaller pore sizes appeared to reduce conspicuously, and the pores of 10～50 mm increased up to 44.6%. During the regeneration, the sulfate has been produced. It is proven that the structure of desulfurizer was not modified too much after regeneration desulfurization from 2 to 5 times of regeneration, and the performance of desulfurizer reached to stability. Therefore, it is concluded that the main factors to the perfommance of the desulfurizer are of both the surface structure of the desulfurizer and the coverage of desulferizer surface with the sulfate in regeneration. And the accumulated sulfur capacity is of 12.8% after six-times of desulfurization and five-times of regeneration, which is 5.56 times that of fresh desulfurizer in one time of desulfurization.