Single-phase β′-SiAlON (Si6−zAlzOzN8−z, z= 0–4.2) ceramics with porous structure have been prepared by pressureless sintering of powder mixtures of á-Si3N4, AlN, and Al2O3 of the SiAlON compositions. A solution of AlN and Al2O3 into Si3N4 resulted in the β′-SiAlON, and full densification was prohibited because no other sintering additives were used. Relative densities ranging from 50%–90% were adjusted with the z-value and sintering temperature. The results of X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses indicated that single-phase β′-SiAlON free from a grain boundary glassy phase could be obtained. Both grain and pore sizes increased with increasing z-value. Low z-value resulted in a relatively high flexural strength.