The determination of the thickness and elemental composition is an important part of the characterization of nanolayered structures. For buried nanolayers, X-ray fluorescence spectrometry is a qualified method for the thickness determination whereas conventional electron emission based methods may reach their limits due to rather restricted information depths. The aim of the presented investigation was the comparison of reference-free X-ray fluorescence spectrometry under conventional and grazing incidence conditions offering complementary information with respect to quantification reliability, elemental sensitivity, and layer sequences. For this purpose, buried boron-carbon layers with nominal thicknesses of 1, 3, and 5 nm have been studied using monochromatized undulator radiation in the laboratory of the Physikalisch-Technische Bundesanstalt (PTB) at the synchrotron radiation facility BESSY II. The results for the two beam geometries are compared and show particulate good agreements, thus encouraging the complementary use of both methodologies.