The charge accumulation phenomenon at the gas–solid interface under the co-action of DC electric field and temperature gradient is of great significance, but its long-time evolution characteristics are still unclear. In this work, the accumulation and dissipation characteristics of the surface charge on the epoxy-SF6 interface within 216 h were obtained, indicating that, (a) the normal surface electric field is increased by the temperature gradient along the gas–solid interface, which results in a prominent increase in the surface charge density; (b) there are different evolution processes of surface charge in high and low temperature regions under the co-action of DC-temperature gradient, and the increase of the charge trap density caused by the degradation of solid material is considered to be an important reason for the charge evolution; (c) the total charge dissipation ratio within 600 s decreases with the increase of charging time in DC electric field, and the surface charge dissipates mainly to the gas side of the interface; (d) the large amount of charge accumulated at the interface distorts the surface electric field at the triple junction points. The total electric field strength at the low-temperature tri-junction point increases by 35.5%, while the direction of the tangential field at the high-temperature tri-junction point reverses during the long-time co-action of the DC-temperature gradient. The results of this work may be helpful to understand the long-time charge evolution characteristics of the gas–solid interface under the DC-temperature gradient and to reveal the failure mechanism of the gas–solid interface.