"Chemical shifts" in core-level photoelectron binding energies are an important feature of conventional laboratory-based x-ray photoelectron spectroscopy (XPS) and indeed are why the technique was originally referred to as ESCA - electron spectroscopy for chemical analysis. For surface studies, however, this ability to exploit XPS chemical shifts is greatly enhanced through the use of modern synchrotron radiation facilities to achieve enhanced spectral resolution and surface specificity. There are now many examples of how such core level shifts alone can distinguish and give insight into the nature of adsorbed and coadsorbed species on surfaces. In addition, however, these chemically-shifted photoemission peaks can be used to provide quantitative chemical-state-specific local structural information by using them to monitor photoelectron diffraction and absorption in x-ray standing waves. For both methods the high spectral brightness, tunability, and ability to provide light in the vacuum ultra-violet and soft x-ray ranges are essential features provided only by synchrotron radiation. These capabilities will be illustrated by a small number of case studies of adsorption and coadsorption systems where the ability to distinguish atoms of the same element in different chemical or structural local environments proved essential to understanding the systems.