AbstractWhen reaction‐bonded silicon nitride containing MgO/Y2O3 additives is sintered at three different temperatures to form sintered reaction‐bonded silicon nitride (SRBSN), the thermal conductivity increases with sintering temperature. The β‐Si3N4 (silicon nitride) crystals of SRBSN ceramics were synthesized and characterized to investigate the relation between the crystal structure and the lattice oxygen content. The hot‐gas extraction measurement result and the crystal structure obtained using Rietveld analysis suggested that the unit cell size of the β‐Si3N4 crystal increases with the decrease in the lattice oxygen content. This result is reasonable considering that the lattice oxygen with the smaller covalent radius substitutes nitrogen with the larger one in the β‐Si3N4 crystals. The lattice oxygen content decreased with increasing sintering temperature which also correlated with increase in thermal conductivity. Moreover, it is noteworthy from the viewpoint that it may be possible to apply the lattice constant analysis for the nondestructive and simple measurement of the lattice oxygen content that deteriorates the thermal conductivity of the β‐Si3N4 ceramics.