This paper presents the effects of accumulation of surface charges on hydrophobic level and the changes of surface potential decay with various artificial environment treatments on high temperature vulcanized (HTV) silicone rubber used for outdoor insulating material. For this study, the charging apparatus by corona discharge, in which grid electrode was installed between the main corona and ground electrode, was used. From this study, it was found that the accumulation of surface charges above a critical surface potential on silicone insulating materials could lead to the temporary loss of surface hydrophobicity. In addition, corona stress and water absorption stress increase the decay rate of surface charges of HTV silicone rubber, while ultraviolet (UV) stress causes longer decay time. We could conclude that the effects of surface charges on hydrophobicity level and the changes of surface state by various artificial treatments were found through a trend of surface potential decay.