The initiation mechanism of flashover along the surface of polytetrafluoroethylene (PTFE) under AC voltage in vacuum was examined. Two distinct phases of light emission were observed, i.e., a stable low-level optical process under low voltage, so-called phase A, and an irregularly intense process called phase B for a light higher voltage. The results suggest that phase A is due to electroluminescence (EL) produced by the recombination of electrons and holes injected from electrodes. A new model has been proposed to explain the optical phenomena in phase B and the developing process of surface flashover.