Functional fillers with low thermal conductivity and high near-infrared reflectance play a vital role in high temperature thermal insulation coatings and make an outstanding contribution to achieving efficient comprehensive thermal insulation. In this work, the thermal insulation and bonding properties of lanthanum–cerium oxide (LCO) coatings were regulated by composition design. The effects of the La/Ce mole ratio on phase composition, the thermal conductivity and near-infrared reflectivity of LCO coatings were investigated systematically. The results showed that coating with a La/Ce mole ratio of 1:1 possess the excellent thermal insulation properties (ΔT ≈ 115°C) due to the formation of a LCO solid solution and a lanthanum phosphate mesophase with low thermal conductivity and high near-infrared reflectivity. In addition, the mortise and tenon structure was formed between the coating and the substrate, which led to the remarkable bonding properties. The LCO coating offers excellent thermal insulation properties and broad application prospects in the fields of high temperature and energy conservation.