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Self‐propagating high‐temperature synthesis (SHS) was applied to synthesize α‐SiAlON powders doped by RE (RE = Eu,Pr,Ce) and codoped by RE and yttrium. The results showed that the weight ratio of α‐SiAlON to (α‐SiAlON +β‐SiAlON) decreased from 70%, 55%, and 25% for europium‐, praseodymium‐, and cerium‐doped α‐SiAlON compositions, respectively, and the weight percentage of α‐SiAlON phase increased to 100% for both (Eu,Y) and (Pr,Y) systems and 94% for the (Ce,Y) system, indicating SHS is a promising approach for synthesizing α‐SiAlONs stabilized by the cations that could not be incorporated into the α‐SiAlON structure by conventional sintering methods.

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