Ligand exchange on gold nanorods (NRs) is still too often dismissed or not given the importance it should deserve. The many applications of gold NRs, mainly in plasmonics, biological imaging, and sensing, are made possible by fi nely tuning not only the optical properties of the metallic core but also the tethered functional groups. Gold NRs are mainly synthesized by using CTAB as the morphology-guiding surfactant, and an intimate relationship between the crystallographic facets of the rod and the CTAB bilayer exists. Because of this, it is imperative to fully understand the ligand exchange mechanisms that allow replacing CTAB with functional ligands, including the energetic contributions. Here, the major applications of gold NRs are briefl y overviewed, and what is known about ligand exchange mechanisms is summarized, as well as why it is important to achieve complete removal of CTAB, including the techniques that are used to characterize the exchange reaction products. The concept of interface in gold NRs is briefl y examined, and explained why the scientifi c community should focus more on understanding and characterizing it. Starting from the published literature, the reader is guided through the reasons why it is thought that ligand exchange on gold NRs is perhaps the next grand challenge in the nanoparticle fi eld.surfactants and reducing agents have been employed to produce gold NRs, but have been shown to not be able to yield the same fi nely tunable control over the morphology if used without CTAB. [ 14 ] In addition, it has been shown that the purity of CTAB highly infl uences the ability to synthesize gold NRs. [ 15 ] Recent work by Wadams et al. [ 16 ] has demonstrated that the NR growth is mostly susceptible to the action of CTAB during the early stages, dominated by epitaxial micellar adsorption of the surfactant and by adatom reorganization. The same authors have also shown that each stage is characterized by thermodynamically stable crystallographic facets at the tips and the sides of the rods that evolve during growth (see Figure 1 ). [ 17 ] Because of these discoveries, the above studies have opened a Pandora's box for the scientists interested in gold NRs. Because CTAB is so intimately connected to our synthetic ability to tune the nanoparticle's morphology, we cannot consider it only a mere surface stabilizer, and hence its replacement with other capping agents through ligand exchange should be considered a complex reaction, whose mechanism needs to be thoroughly understood via carefully devised thermodynamic studies. Ligand exchange is often employed as a tool to functionalize the NRs for a specifi c application and it is only rarely the primary subject of investigation. Many of the applications of gold NRs, whether in plasmonics or biological imaging, are closely dependent upon our ability to tailor their surface functionalization and tune their properties. However, the lack of understanding of ligand exchange will most likely negatively impact our ability to employ NRs in technological appl...