The article presents the results of a study of characteristic X-ray spectra of free atoms by means of a new simple technique. A pulsed electron beam was used for evaporation and to create inner-shell vacancies in free atoms of metals. The spectra were obtained with the help of an X-ray monochromator which allowed precise comparison between the free-atoms spectra and corresponding solid-state spectra. The shifts of the peaks were measured and found to be in the range Δλ/λ≈10−5–10−4. The K-, L- and M-series spectra were studied. A number of the free-atoms spectra revealed structure which was not resolved in the solid-state spectra and which is of interest for atomic structure calculation applications. This electron beam technique for the investigation of X-ray characteristic spectra of free atoms can be used for the refinement of X-ray wavelength standards.