We have carried out angle-resolved photoemission spectroscopy (ARPES) and spectromicroscopy studies to understand the metal–insulator transition (MIT) observed in sodium tungsten bronzes, Na_𝑥WO₃. The experimentally determined band structure is compared with the theoretical calculation based on full-potential linear augmented plane-wave method. It has been found that there is a good gross agreement between experiment and theory. ARPES spectra on the insulating sample show that the states near 𝐸_F are localized due to the random distribution of Na in WO₃ lattice which causes strong disorder in the system. Our spectromicroscopy measurements on both insulating and metallic samples do not approve percolation model to explain MIT in Na_𝑥WO₃. Photoemission spectroscopy on metallic samples does not show any Na-induced impurity band (level), which was one of the models to explain MIT. Electron-like Fermi surface(s) has been found from our experiment for metallic samples at the 𝛤(X) point which shows good agreement with band calculation.