There is a wide range of application requirements of high-infrared-reflectance materials, like laser, marine, aerospace industry and military. Although metal materials have high reflectivity, oxidation and low melting point limit its applications. Ceramic materials have high melting point and good thermal stability, but their wide band gap always leads to low reflectivity. Thus, we designed a series of high-reflectance ceramics with perovskite structure based on first-principles calculations. The results show that in small doping conditions, the Fermi level appears in the conduction band and the electronic state near Fermi level increased, which contributes greatly to the improvement of reflectivity. The calculation reflectivity of Ba0.5Sr1.5SmTaO6 and Ba1.5Sr0.5SmTaO6 is up to above 99%, which is comparable to metal materials. Through this study, we provide a series of potential materials that can replace metal materials service at higher temperature and atmospheric environment.