Using the method of X-ray photoelectron spectroscopy, the electronic structure of amorphous metallic Fe$_{82}$Si$_{4}$B$_{14}$ alloy is investigated. As shown, the preparation of the amorphous Fe$_{82}$Si$_{4}$B$_{14}$ ribbon by rapid cooling of the melt generates the oxidized surface layer. A good solubility of boron in the film and a slight segregation of silicon within the investigated alloy are determined. The amorphous Fe$_{82}$Si$_{4}$B$_{14}$ alloy is characterized by the oxidized surface layer with an estimated thickness of about 100 nm. Both the C—C bonds and complex carbon compounds such as C=O are revealed in this layer. In the oxidized layer, the boron compounds are present in trace amounts. A significant surface segregation of Si is observed; the concentration of Si is kept constant in the oxidized layer and in the bulk of investigated ribbon. Iron in the oxidized layer is chiefly represented by oxides. In the bulk of film, the presence of silicon carbide, SiC, and a minor amount of oxygen and nitrogen are detected. Carbon is revealed on the surface of the amorphous metallic alloy mainly in oxidized state, while in the bulk, it is in the form of silicon compounds (most probably as silicon carbide).