AFM & STM metrology has been around for a long time, and especially intense since it has been awarded by the Nobel Prize in Physics in 1986. Since then, many AFM & STM groove profile measurements on surface relief diffraction gratings have been presented. However, a wide review of the results of the use of AFM & STM methods for groove metrology of various surface relief gratings has not really been undertaken. The following problems are discussed in this chapter: the cantilever tip deconvolution, geometry, and radius; groove shapes and abrupt groove slopes; roughness; PSD functions; etc. Also, the author demonstrates comparisons with other widely-used metrology techniques and examples of AFM & STM data of bulk, coated, and multilayer-coated ruled, or holographic, or lithographic gratings having realistic groove profiles. These gratings were chosen because high quality efficiency data exists, in particular, for space gratings or/and X-ray gratings characterized by synchrotron radiation sources; and their groove profiles, together with random nanoroughness, were measured by AFM or STM to be included in rigorous efficiency and scattered light intensity calculus. In the present chapter, both the earlier published results and the recent, non-published yet results are described and discussed.