Superior thermal quenching and degradation of phosphors are required for long lifetime lighting devices, such as light-emitting diodes, which can be realized through composition modification. Here, Al-N bonds in AlON: Eu²⁺ phosphors are substituted by higher bond order of Si-C. Photoluminescence (PL) results show thermal quenching (at 150 °C) and thermal degradation (after 600 °C treatment in air) are improved by 5% and 8% with a small decrease of PL intensity in 5% SiC doped AlON: Eu²⁺ phosphor. To explain these observations, first-principles computational study was performed to understand the Si and C configuration in AlON:Eu²⁺. The calculations reveal that Si and C elements are not randomly distributed in AlON lattice. It was found that Si prefers occupying tetrahedral sites (Td-Si) and the insertion of C in Td-Si is always energetically favorable, which results in the formation of SiC₄ and SiNC₃ clusters. Thus, the Al-N substitution by Si-C induces a stronger local structure, which accounts for the emission redshift and better thermal stability.