Solar thermal power generation is one of the effective ways to utilize solar energy. It plays an important role in alleviating energy crisis and environmental pollution and has far-reaching social significance. The selective absorption coating is an important part of solar collecting tube, and the key factor to determine the conversion efficiency of solar energy and heat energy. In order to characterize the optical properties of solar selective absorption coatings under high temperature conditions, a new method for measuring the spectral absorptivity of high temperature metal-ceramic selective absorption coatings was proposed. Based on Fourier spectrometer with double detector and integrating sphere with heating function, a high-vacuum measurement device was developed, which has the function of high temperature oxidation resistance and working temperature simulation. The Mo-SiO2 selective absorption coating with the typical double absorption layer, prepared by magnetron sputtering, was used as the sample for measurement. In addition, the solar spectral absorptivity of sample at different temperature was measured in the spectral range of 0.3～2.5 μm and temperature range from room temperature to 700 ℃. Measurement values at the room temperature were compared to the values calculated from the effective medium theory and matrix formula, and results show a good consistency. Because the maximum deviation is only 2.9%, the feasibility of measurement method is verified. The measurement of high temperature spectral absorptivity has important guiding significance and promoting function for optimization of design parameters and enhancement of absorption performance.