The phase analysis of sodium azide (NaN3) has been investigated by in situ synchrotron X-ray diffraction measurements in a diamond anvil cell up to 52.0 GPa at room temperature. Three pressure-induced phase transitions were observed. The phase transition pressures were determined to be 0.3, 17.3, and 28.7 GPa verified by three different pressure transmitting media. The first high pressure phase, α-NaN3 (0.3 ∼ 17.3 GPa), was identified to be monoclinic with a C2/m space group. The β-NaN3 to α-NaN3 transition is a second-order phase transition, accompanied by the shearing of the Na-layers and the tilting of the azide chains. The second high pressure phase, γ-NaN3 (18.4 ∼ 28.7 GPa), has a lower symmetry than the α-NaN3. A further phase transition of γ-NaN3 to δ-NaN3 at 28.7 GPa was observed.