The performance of multilayers at the X-UV wavelengths depends upon the structural and geometrical imperfections of the deposited materials. These two respective contributions are not easily separated when only one Bragg peak is recorded, as is usually the case in the X-UV range, so a prediction of the performance at other wavelengths appears rather doubtful. We show how grazing incidence X-ray reflectometry (using Cu Kα1 radiation) allows the precise evaluation of both interfacial roughnesses and thickness errors, as well as their variations through the stacks. As examples, we analyse three (W/C) multilayers with periods between 3 to 6 nm and up to 40 layers