The microstructure of molten marks changes according to ambient temperatures, when a short circuit occurs. Investigation of microstructural changes is important for understanding the properties of copper and examining the cause of a fire. In this study, the boundary characteristics and grain-size distribution of molten marks—primary-arc beads (PABs), which short-circuited at room temperature (25 °C), and secondary-arc beads (SABs), which short-circuited at high temperatures (600 °C, 900 °C)—were compared using electron backscatter diffraction. The distribution of Σ3 boundaries was compared, and it was found that SABs have a higher fraction of Σ3 boundaries than PABs. Moreover, it was confirmed that the ratio of maximum grain size (area) to the total area of the molten mark in SABs is larger than that in PABs. Thus, reliable discriminant factors were suggested, such as the fraction of Σ3 boundaries and normalized maximum grain size, which can distinguish PABs and SABs. The four discriminant factors, such as the (001)//LD, GAR, fraction of Σ3 boundaries, and fraction of maximum grain size to the total molten-mark area, were verified using the machine learning of t-SNE and Pearson correlation analyses.