Ice flashover threatens the security and reliability of power transmission. However, the ice flashover mechanism of insulators remains poorly understood. This study analyses water droplet freezing and ion distribution in ice layer under alternating electric field. It also investigates ion migration during icing process of insulator string under alternating electric field and its effects on insulator flashover. Results showed that the average freezing time of water droplets was related to electric field strength. The extent of ion migration during freezing decreased with increasing electric field strength. The maximal melting water conductivity of the ice layer and icicle of the insulator formed under energized condition was higher than the corresponding freezing water conductivity but lower than that under non-energized condition. Furthermore, the hanging location of each insulator significantly affected the melting water conductivity of the ice layer. The surface conductivity of the ice layer increased because of the conductive ion migration in freezing water during freezing, which was an important factor that decreased the flashover voltage of the ice-covered insulator. The existence of alternating electric field would impact the extent of ion migration. This study may serve as a reference for updating prediction flashover model of ice-covered insulators during the melting period.