Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to study short range order in heterometallic alloys for almost four decades. In this critical review, experimental, theoretical and data analytical approaches are revisited to examine their power, and limitations, in studies of bimetallic nanocatalysts. This article covers the basics of EXAFS experiments, data analysis, and modelling of nanoscale clusters. It demonstrates that, in the best case scenario, quantitative information about the nanocatalyst's size, shape, details of core–shell architecture, as well as static and dynamic disorder in metal–metal bond lengths can be obtained. The article also emphasizes the main challenge accompanying such insights: the need to account for the statistical nature of the EXAFS technique, and discusses corrective strategies.