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The expanded ammonium nitrate (EAN) samples with different states were prepared by using a vacuum crystallizing technology. The structure characters, such as porosity, pore structure, specific surface area, particle surface shape and surface defects, and detonator initiation sensitivity and explosion power, of common ammonium nitrate (AN) and EAN were tested using density measuring, N2 adsorbing, scanning electron microscope (SEM) and plate trace test methods. The tested results show that the particle surface of common AN is smoother, denser, lower porosity and specific surface area than those tested of EAN. The particle surface of EAN is irregular, which has edges, protuberance and severely distorted crystal form, and its specific surface area and porosity are larger than those of un-expanded AN. EAN has typical self-sensitization structure characters. The detonator initiation sensitivity and explosion power of ammonium nitrate-fuel oil(ANFO) made of different states of EAN are related to the self-sensitization structures of EAN, and expanded ANFO sample has higher detonator initiation sensitivity and explosion power compared with un-expanded ANFO sample. The characterization techniques can be used to reveal the self-sensitization structure of EAN.