Total reflection X-ray fluorescence (TXRF) spectrometric analysis is basically an energy dispersive technique with the excitation of the sample at grazing incidence geometry. TXRF is a powerful analytical tool for trace element determination, but there is a permanent demand from various scientific disciplines, as well as from the application side, for improved limits of detection (LOD). In light matrices of samples from environmental, medicinal and industrial origins, ng g^–1 concentrations or pg amounts can be reached with TXRF. Regarding the impurities on the surface of Si wafers for ultra large scale devices, fg levels of medium Z elements corresponding to 10⁷ atoms cm^–2 have to be determined. Several approaches to the excitation process are presented: choice of an appropriate anode material and type, high powered X-ray tubes and multilayer monochromators; and synchrotron radiation (SR). The outstanding features of SR are energy tunability over a wide energy range and a linear polarized beam with natural collimation and a high flux of photons on the sample, leading to detection limits of 13 fg for Ni. The optimized experimental setup for an SR-TXRF spectrometer for versatile use will be presented. The results from measurements on intentionally contaminated Si wafers for low and medium Z elements and LODs achieved will be given. To demonstrate the range of detectable elements, spectra from elements C to U after K-shell excitation will be presented.