Abstractα‐SiAlON ceramics with different stabilizing ions of Yb, Dy, Nd, Y, Ca, and binary stabilizing ions of (Yb + Ca) and (Yb + Nd) were prepared by spark plasma sintering at 1600°C and gas pressure sintering at 1800 and 1900°C, and their thermal conductivity was investigated. It was found that α‐SiAlON ceramics with larger and heavier stabilizing ions had lower thermal conductivity and the thermal conductivity could be further reduced by using binary stabilizing ions, which can be explained by phonon scattering from point defects. At the same time, the samples prepared at lower sintering temperatures showed smaller grain sizes and lower thermal conductivity. The relationship between the thermal diffusivity of samples and temperature was studied, where the dependence of inverse thermal diffusivity on temperature was better fitted by a quadratic fitting function than the usual linear one over a wide temperature range from 25 to 800°C.