X-ray absorption fine-structure (XAFS) spectroscopy has evolved in several directions from the late 1970s to the present. Different geometric beam configurations as well as the choice of either electrons or fluorescent photons to detect the energy-dependent variation of the photoelectric cross sections have optimized both the discrimination capability and the detection sensitivity of XAFS. For the cases of surfaces, interfaces, thin and ultrathin films, as well as multilayers, the methodological development is presented with respect to near-edge XAFS, aiming at the speciation of an element, and extended XAFS, providing complementary coordination information.