This paper aims to clarify the phase composition in each sub-layer of tandem absorber TiMoAlON film and verify its thermal stability. The deposited multilayer Ti/(Mo-TiAlN)/(Mo-TiAlON)/Al2O3 films include an infrared reflectance layer, light interference absorptive layers with different metal doping amounts, and an anti-reflectance layer. The layer thicknesses of Ti, Mo-TiAlN, Mo-TiAlON, and Al2O3 are 100, 300, 200, and 80 nm, respectively. Al content increases to 12 at.% and the ratio of N/O is nearly 0.1, which means nitride continuously changes to oxide. According to X-ray Diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) results, the diffraction peak that appears at 2θ = 40° demonstrates that Mo element aggregates in the substitutional solid solution (Ti,Al)(O,N) columnar grain. TiMoAlON films have low reflectivity in the spectrum range of 300–900 nm. When Al content is more than 10 at.%, absorptivity is almost in the spectrum range from visible to infrared, but absorptivity decreases in the ultraviolet spectrum range. When Al content is increased to 12 at.%, absorptivity α decreases by 0.05 in the experimental conditions. After baking in atmosphere at 500 °C for 8 h, the film has the highest absorptivity when doped with 2 at.% Mo. In the visible-light range, α = 0.97, and in the whole ultraviolet-visible-light near-infrared spectrum range, α = 0.94, and emissivity ε = 0.02 at room temperature and ε = 0.10 at 500 °C.