Overcharge is one of the main factors that lead to thermal runaway of lithium batteries. However, there is no research on the quantitative relationship between overcharged state and gas production, so as to effectively monitor the safe state of the battery and avoid thermal runaway. In this paper, X-ray computed tomography (CT) is proposed to explore the overcharge battery. The internal structure changes of bulge deformation and electrode separation is observed from tomographic images of two different cross-sectional directions. The relationship between gas production and overcharge state of charge (SOC) is quantitatively analyzed. As overcharge SOC increases, gas production increases exponentially. Gas distribution is analyzed by density distribution feature (DDF) vector. The gas production is mainly distributed in the middle of the overcharge batteries. It is envisaged that these techniques can be used to better understand the overcharge of battery nondestructively, visually and effectively, then will lead to avoid the occurrence of thermal runaway.