The thermal insulation effect of the coating was closely related to the content of the thermal insulation filler, but too much filler would cause interfacial compatibility problems of various substances in the coating, micro-defects in the coating, and affect the anti–corrosion performance of the coating. Therefore, solving the interface problem was the key to preparing a coating with heat insulation and anticorrosion functions. In this study, organic–inorganic hybrid polymer was used to modify the surface of vacuum ceramic microbeads, and epoxy–silicone resin was used as the film–forming material to prepare a heat-insulating and anticorrosive coating that can withstand 200 °C. The SEM morphology showed that the interface compatibility of the vacuum ceramic beads modified by the organic–inorganic hybrid agent and the film-forming material were improved, the dispersibility was significantly improved, and the beads were tightly arranged; the thermal conductivity of the coating reached 0.1587 W/(m·K), which decreased by 50% after adding 20% ceramic beads, ANSYS finite element simulation showed that the coating has good thermal insulation performance; after the coating underwent a thermal aging test at 200 °C for 600 h, the microstructure was dense, and the low-frequency impedance modulus was still around 109 Ω·cm2. There was no obvious defect in the microstructure after the alternating cold and heat test for 600 h; the low-frequency impedance modulus was still above 108 Ω·cm2, and the low-frequency impedance modulus of the coating was 1010 Ω·cm2 after the 130d immersion test, indicating that the coating had good heat resistance and anti-corrosion performance.