Abstract The purpose of this study is to compare the investigations of amorphous magnetic ribbons combining the usual structural methods with physical impedance spectroscopy (PIS) and X-ray photoelectron spectroscopy (XPS). The samples are commercially available rapidly quenched ribbons for torroidal transformers. Two types of ribbons were thermally treated below the temperature of amorphous–crystalline phase transition. Two binding energies of B 1 selectrons are determined by XPS in one of the as-quenched ribbons, which show impedance time constant spectra without dispersion. The other ribbon, possessing only one value of binding energy of the B 1 selectron (B Istate) in a rapidly as-quenched state, undergoes transition to a still amorphous state but acquires high electromagnetic losses and show another value of the binding energy of the B 1 selectron (B IIstate) after the heat-treatment procedure. This latter type of ribbons show structural impedance spectra containing various time constant values.