Abstract Subnanometer, atomically precise thiolate-protected gold nanoclusters represent an important advancement in our understanding of thiolate-protected gold nanoparticles and thiolate-gold chemistry. Aside from being a link between larger gold nanoparticles and small gold complexes, gold nanoclusters exhibit extraordinary molecule-like optical, electronic, and physicochemical properties that are promising for next-generation imaging agents, sensing devices, or catalysts. The success in elucidating a number of unique thiolate-gold surface and gold core structures has greatly improved our understanding of thiolate-gold nanoclusters. Nevertheless, monitoring the structural and electronic behavior of thiolate-protected gold nanoclusters in a variety of media or environments is crucial for the next step in advancing this class of nanomaterials. Not to mention, there are a number of thiolate-protected gold nanoclusters with unknown structures or compositions that could reveal important insights on application-based properties such as luminescence or catalytic activity. This review summarizes some of the recent contributions from X-ray absorption spectroscopy (XAS) studies on the intriguing bonding properties of thiolate-protected gold nanoclusters and some structural analogs. Advantages from XAS include a local structural, site- and element-specific analysis, suitable for ultra-small particle sizes (1–2 nm), along with versatile experimental conditions.