In order to study the laser radiation effect on Octogen （HMX） crystal， various technical methods were used to characterize the microstructure evolution of HMX crystal under 360 nm ultraviolet laser. By optical microscope， the process from accumulation of defects to cracking under laser irradiation was observed in HMX crystals. In-situ Raman spectroscopy demonstrated that the absorption of UV photons would stimulate HMX molecules， causing the ring vibration. In-situ wide-angle X-ray scattering （WAXS）， single crystal X-ray diffraction （SCXRD） and in-situ small-angle X-ray scattering （SAXS） were also adopted to study the crystal changes and defects evolution of HMX under UV laser irradiation. It is found that phase transformation does not happen but some new defects generate in HMX. The in-situ SAXS results show that the pores in HMX increase continuously after 1170 minutes of laser irradiation and a bimodal distribution exists in the region ranging from 10 to 20 nm and 30 to 40 nm， respectively. During the laser irradiation process， small pores in HMX keep accumulating and gradually merge into larger pores. Due to the accumulation of defects， the microcosmic pores extend into micro-cracks， and then expand into macro-cracks.