High emissivity coatings with sol as the binder have the advantages of room temperature curing, good thermal shock resistance, and high emissivity; however, only silica sol has been used in the current systems. In this study, aluminum sol was used as the binder for the first time, and MoSi2 and SiC were used as emittance agents to prepare a high emissivity MoSi2-SiC-Al2O3 coating on mullite insulation tiles. The evolution of structure and composition at 1000–1400 °C, the spectral emissivity from 200 nm to 25 μm, and the insulation performance were studied. Compared with the coating with silica sol as a binder, the MoSi2-SiC-Al2O3 coating has better structural uniformity and greater surface roughness and can generate mullite whiskers at lower temperatures. The total emissivity is 0.922 and 0.897, respectively, at the wavelength range of 200–2500 nm and 2.5–25 μm, and the superior emissivity at a low wavelength (<10 μm) is related to a higher surface roughness and reduced feature absorption. The emissivity reduction related to the oxidation of emittance agents at a high temperature (−10.2%) is smaller than that of the silica-sol-bonded coating (−18.6%). The cold surface temperature of the coated substrate is 215 °C lower than the bare substrate, suggesting excellent thermal insulation performance of the coating.