High absorptivity and low emissivity are characteristics needed in an ideal solar selective absorber. In high-temperature applications, such as a solar concentration power system in which the solar surface works under a long-term high temperature (about 400 to 800 °C), the absorber material has to maintain high absorption in the visible region, high reflectance in the infrared region, and excellent thermal stability at high temperature. In this research, the design of a molybdenum-based (Mo-based) solar selective absorber was analyzed by the admittance locus method, and the films were deposited by magnetron sputtering. The ratio of the extinction coefficient to the refractive index of the Mo layer was close to 1, so that the Mo-based solar selective absorber had a broad absorption band, high absorption, and good solar selectivity. Its average reflectance in the visible region was less than 0.4%. The experimental absorption was 97.1% (simulated absorption was 98%) and the emissivity was from 13% to 20% (simulated emissivity was 8% to 26%) as the temperature increased from 400 to 800 °C.