Transmission electron microscopy was employed to study the crystallographic evolution of discharge product Li2O2,Li2O,LiOH and Li2CO3 in Lithium-oxygen batteries under the electron beam irradiation. The irradiation damage phenomena of the Li2O2,Li2O,LiOH and Li2CO3 were observed under the electron beam irradiation. By the method of in-situ selected area electron diffraction and electron energy loss spectroscopy,the structure of Li2O is found to remain unchanged under the electron beam irradiation,but the structures of Li2O2,LiOH and Li2CO3 turned into Li2O. Li2CO3 is the most stable one,then Li OH and Li2O2. Li2CO3 sample is directionally dependent on electron irradiation. The [001] direction performs a higher resistance on radiation damage than [103]direction. With the increase of electron radiation dose,Li2CO3 sample has a shorter anti-radiation time and higher damage degree.