SiAlON ceramics have found applications in many different areas due to their excellent engineering properties such as high hardness, fracture toughness, good thermal shock and oxidation resistance. SiAlON exist mainly in two different polymorphs: a (MxSi12-(m+n)Al(m+n)OnN16-n; M: metal and rare earth cations, x≈0,35 and n≤1,35) and β (β-Si6-zAlzOzN8-z; 0≤z≤4). In general, stable alpha and beta phases separately as well as in combination of α and β are obtained by incorporation of metal and rare earth cations as sintering additives. The metal cations such as Li, Mg, Ca, Y, and most lanthanide cations with the exception of La, Ce, Pr and Eu are able to stabilise α-SiAlON structure. Ekstrom et al. 1991 found that cerium can not occupy interstitial sites in α-SiAlON structure due to the fact that ionic radius of Ce3+ (0.103 nm) is too large, whereas ionic radius of Ce4+ (0.080 nm) is too small to stabilise α-SiAlON structure. After this work, several studies carried out to incorporate cerium cations into α-SiAlON structure. It was shown that cerium cation alone can be incorporated into α-SiAlON if the samples are either fast cooled after sintering, or when the samples are spark plasma sintered. On the other hand, cerium can also be incorporated into the α-SiAlON structure when it is used as a sintering additive together with a smaller α-SiAlON stabiliser cation such as Yb or Ca. Similar results were observed in other multi-cation doped SiAlONS that non α-SiAlON stabiliser cations like Sr2+ (0.112 nm) and La3+ (0.106 nm) are able to stabilise α-SiAlON when used together with α-SiAlON stabiliser cations such as Ca or Yb. Although it was shown that cerium existed in mixed valance state at domain boundaries in Ce-doped and spark plasma sintered α-SiAlON, there is no work on the valance determination of cerium in sintered α-SiAlON which has no domain boundaries. Therefore, in this study; it was aimed to incorporate cerium into α-SiAlON structure by combining with Yb3+ and the determination of possible cerium valence states (Ce3+/Ce4+) in both α-SiAlON grains and secondary phases.