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Rare‐earth‐doped oxynitride or nitride compounds have been reported to be luminescent and may then serve as new phosphors with good thermal and chemical stabilities. In this work, we report the photoluminescence (PL) spectra of europium‐, terbium‐, and praseodymium‐doped Ca‐α‐SiAlON ceramics. The highly dense ceramics were prepared by hot pressing at 1750°C for 1 h under 20 MPa in a nitrogen atmosphere. Europium‐doped Ca‐α‐SiAlON displayed a single broad emission band peaking at λ= 550–590 nm depending on the europium concentration. The emission bands in the spectra of europium‐doped Ca‐α‐SiAlONs were assigned to the allowed transition of Eu²⁺ from the lowest crystal field component of 4f⁶5d to ⁸S_7/2 (4f⁷) ground‐state level. The emission spectra of terbium‐ and praseodymium‐doped Ca‐α‐SiAlON ceramics both consisted of several sharp lines, which were attributed to the …