A planar aperiodic metal-dielectric multilayer structure consists ofCr/AlCrN/AlCrNO/AlCrN/AlCrNO/AlCrO multilayers was preparedusing cathodic arc ion plating. The spectral performance and long-termthermal stability in air were investigated with the aim of designing highperformance solar selective absorbing coatings for photo-thermal conversionat high temperatures. The as-deposited multilayer coating exhibitsa high absorptance of 0.90 and a relatively low emittance of 0.15,as well as an outstanding thermal stability with a selectivity of 0.94/0.10 even after annealing at 500 °C for 1000 h in air. The enhancementin absorptance after annealing is attributed to the formation of smallamounts of AlN, CrN and Cr2N nanocrystallites in the AlCrN andAlCrON amorphous matrices, which can effectively scatter the incidentlight into a broadband wavelength range, increasing the optical pathlength in the absorbing layers. The pretty low infrared emissivity afterannealing is resulted from the formation of a handful of Cr2O3 andAl2O3 nanograins embedding in the amorphous AlCrO antireflectionlayer, which can efficitively reflect the solar infrared radiation and thethermal emittance of the substrate. The good thermal stability is possiblydue to the excellent thermal stability of the cermet-based amorphousmatrices and the sluggish atomic diffusion in the nanoparticles,which effectively slow down the inward diffusion of oxygen and avoidfurther agglomeration of naonparticles. These results suggest that themultilayer coating developed in this study could be possibly applied forphoto-thermal conversion at high temperatures.