The microscopic characteristics of melting trace caused by copper wire fault are an important basis for the physical evidence identification of electrical fires. Metallography is an important method in electrical fire research, and computer-aided quantitative analysis on metallographic structure is common in materials aspect. In this study, the metallographic structure and phase composition characteristics of melting trace caused by overcurrent fault were explored with the aid of a metallographic microscope and an X-ray diffractometer (XRD). The results show that the grains are mainly slender dendritic and columnar crystals when the current is 128 A, while they are coarse dendritic and cellular crystals when the current is greater than 192 A; the average grain diameter of melting trace of copper wire grows with the increase in current. The main phases of melting trace caused by overcurrent fault of copper wire are α-Cu base and Cu2O, and the new phases Cu4Si and Cu2Mg are formed when the current is higher than 160 A. In addition, the solidification process of metallographic structure of copper wire under different currents was simulated by the Procast software. It is found that the simulation results are basically in agreement with the experimental data, which suggests that this model can effectively predict the microstructure characteristics of melting trace of copper wire under different currents. The research results can provide a sound basis for the physical evidence identification of electrical fire and improve the accuracy and scientificity of electrical fire investigation.