Chemical composition and electronic structure of the native-oxide-covered AlxGa1–xAs(100) (x ∼ 0.3) surfaces were investigated by x-ray photoelectron spectroscopy and photoluminescence before and after treatment at room temperature with a concentrated aqueous solution of sodium sulfide in order to get inside into mechanism of sulfide solution interaction with aluminum-containing III–V alloys. Even short treatment of the n-AlGaAs(100) surface leads to the removal of the most of the native oxide layer so that the surface is covered with a thin layer of residual aluminum and gallium oxides with a thickness of approximately 1 ML, which can be formed during air exposure after termination of the chemical treatment. Longer treatment of the n-AlGaAs(100) surface does not further reduce the amount of residual aluminum and gallium oxides. The etching of native oxide layer on the p-AlGaAs(100) surface proceeds slower and the lowest amount of residual aluminum and gallium oxides is achieved after etching for 12 min. At the same time sulfur is hardly adsorbed at the AlGaAs(100) surfaces after interaction with the solution. It is found that the lower the amount of residual aluminum and gallium oxides on n- and p-AlGaAs(100) surfaces, the higher is the photoluminescence intensity. The band bending on the native-oxide-covered n- and p-AlGaAs(100) surfaces is about 0.85 and 0.5 eV, respectively, while the ionization energy is nearly the same for both surfaces. Treatment of n- and p-AlGaAs(100) surfaces with an aqueous sodium sulfide solution causes simultaneous decrease in their ionization energy.