A method using the atom–vacancy ordering phenomenon for the visualization of structural vacancies in crystals was suggested and implemented. The ordered nonstoichiometric titanium monoxide Ti5O5 was taken as the object of investigation, because the structural vacancies in this compound can be observed due to the formation of continuous vacancy channels in certain crystallographic directions. The structural vacancies in the specially oriented sample of ordered titanium monoxide were directly observed by high-resolution transmission electron microscopy with a magnification of 4 × 106