A new method to detect energy‐band bending using x‐ray photoemission spectroscopy has been proposed which measures the changes in the binding energy with the change in the detection angle of photoelectrons. This method was applied to crystalline silicon of various doping conditions with a thin surface oxide and after removing it by ion sputtering. The change in the binding energy with the change in the detection angle was observed only in heavily dopedp‐type silicon before sputtering, but not in other silicon specimens studied in this work. All specimens showed an identical binding energy independent of the detection angle after removing surface oxides by sputtering. These results are explained semiquantitatively using a simple band‐bending model.