Metal clusters comprise an important class of functional nanomaterials due to their tuneable size, structure, shape and support, which are key factors that affect their physicochemical properties and functions. In cluster research, the main objectives are the design of new materials with the desired properties and the development of new methods for characterizing these materials. In this chapter, methods of extended X-ray absorption fine-structure (EXAFS) analysis developed in the last two decades for the structural characterization of monometallic and bimetallic nanoclusters are reviewed.