Enhancing the stability of spectrally selective coatings (SSC) at high temperatures in air is necessary to push the concentrated solar power (CSP) technology to the next level. To avoid failures that might not be discovered for years, advanced knowledge of the chemical properties related to the degradation mechanisms with temperature is required. For this purpose, the Mo local environment is investigated here for Mo−Si 3 N 4 and MoSi 2 − Si 3 N 4 nanocomposites SSCs. The atomic short-range order around Mo proves that MoSi 2 is the stable form that appears in high temperature vacuum annealing and that MoO 3 formation is associated with optical degradation in air annealing. Deposition of Al 2 O 3 capping layers with different techniques is found of paramount relevance in the long term performance of MoSi 2 −Si 3 N 4 based SSCs. MoSi 2 −Si 3 N 4 hybrid composite with Al 2 O 3 capping layer shows exceptional functional stability even after 2900 h at 600 °C in air. Antireflective Al 2 O 3 layer synthesized by atomic layer deposition (ALD) shows an extraordinarily efficient protection against oxidation with unprecedented MoSi 2 stability in MoSi 2 −Si 3 N 4 hybrid composite, and optimum long-term optical performance. On the other hand, Al 2 O 3 layer deposited by sputtering blocks the formation of detrimental MoO 3 at 600 °C but allows the formation of MoO 2 in MoSi 2 −Si 3 N 4 for long annealing times which, however, also provides excellent and stable optical functionality related to MoO 2 high stability. KEYWORDS: spectrally selective coating (SSC), concentrated solar power (CSP), solar selective absorbers, high temperature air stability, MoSi 2 −Si 3 N 4 nanocomposite, Al 2 O 3 capping layer, aging