A new application of a centerless x-ray diffractometer was proposed that goes beyond residual stress measurements during the regular operation of such equipment. During depth residual stress measurement, it is possible to fit the measured interference function of the ferrite (211) with a different number of curves as a function of depth. The different curves corresponded with the appearance of ferrite fractions with different grain sizes and concentrations in ferrite, perlite, bainite, or martensite. Accordingly, different microstructures were non-destructively detected through the thickness of the carburized layer, and a good correlation was found with results from metallography and hardness testing. This novel method was validated on solid and gas carburized samples, but more work is needed to apply it to other microstructures.