Nano zinc oxide with a high refractive index has good thermal reflection performance, hollow glass microspheres have good thermal reflection and insulation performance, and sepiolite nanofibers with many nanostructural pores have good thermal insulation performance. The dispensability of nano zinc oxide in coating materials was improved by optimizing surface silane coupling agent modification process, leading to the good thermal reflection performance. The thermal insulation performance was improved by hollow glass microspheres and sepiolite nanofibers. On this basis, the thermal insulation coating materials were prepared by exploring the effect of amount, complex mode, and other factors of the above three kinds of functional fillers on the thermal reflection and insulation performance of coating materials. The results showed that the surface modification effect of nano zinc oxide was the best when the silane coupling agent addition was 6%. The reflection and insulation performance of the coatings were the best when the additions of modified nano zinc oxide, hollow glass microspheres, and sepiolite nanofibers were 3%, 4%, and 4%, respectively. Compared with the control coating materials, the thermal insulation effect was improved obviously, which was evaluated by the -13.5 degrees C increase of maximum temperature difference between the upper and the lower surfaces.