To nondestructively evaluate the layer structure and the interface roughness of a multilayer film as a sample, with the multilayer film being irradiated with X-rays.

In the method of evaluating the multilayer film, the multilayer film as the sample is irradiated with the X-rays of a prescribed energy (or a prescribed wavelength), the dependence on the incident light energy (or the wavelength) of the amount of a sample current flowing in the multilayer film is measured, an electronic yield X-ray standing-wave spectrum is measured, and the layer structure and the interface roughness are evaluated on the basis of the shape of the spectrum.