Surfaces-and interfaces-are ubiquitous at the nanoscale. Their relevance to nanoscience and nanotechnology is therefore inherent. Colloidal inorganic nanocrystals (NCs), which can show more than a half of their atoms at the surface, are paradigmatic of the role of surfaces in determining materials' form and functions. Therefore, colloidal NCs may be regarded as soluble surfaces, allowing convenient study of ensemble structure and properties in the solution phase.Colloidal NCs commonly bear chemical species at their surface. Such species (generally referred to as ligands) are introduced already in the synthetic procedures and are added postsynthesis in surface chemistry modification (ligand exchange) reactions. Ligands (i) affect the reactivity and diffusion of the synthetic precursors, (ii) mediate NC interactions with the surroundings, and (iii) contribute to the overall electronic structure. In principle, a vast amount of ligands, as large as our imagination, could be used to coordinate the surface of colloidal NCs. In practice and despite the plethora of studies on NC surface chemistry, a relatively limited number of ligands have been explored. In addition, the importance of designing a set of ligands with tailored features (a ligand library), which may permit comprehensive discussion and explanation of the role of surfaces in the NC structure and properties, is often overlooked. Ligand libraries may also foster heuristic access to novel, unexpected observations.Here, the rational design of ligand libraries is discussed, suggesting that it may be a general method to advance knowledge on colloidal NCs and nanomaterials at large.First, a general ligand framework is introduced. The main subunits are identified: ligands are constituted by a binding group and a pendant moiety, bearing functional substituent groups. On this basis, ligand binding at the NC surface is discussed borrowing concepts from coordination chemistry. Dynamic equilibria at the NC surface are highlighted, revealing the compromise between forming and breaking bonds at interfaces and its intricate interplay with the surroundings. Tailoring of the ligand subunits may impart functions to the whole ligand, eventually transposable to the ligated NC.On these bases, it is shown how ligand design may be exploited to (i) exert control on the size and shape of the NCs, (ii) determine NCs' dispersibility in a solvent and affect their self-assembly, and (iii) tune the NCs' optical and electronic properties. These observations point to a description of colloidal NCs as un-decomposable species: ligands may be conceived as an integral part of the overall chemical and electronic structure of the colloidal NC and should not be considered as mere appendages that weakly perturb the inorganic core features.Finally, a perspective on the ligand library design is given. Function-oriented design of the ligand subunits is foreseen as an effective strategy to explore the chemical diversity space. High-throughput screening processes by using computation may represent a valuable tool for such an exploration. The whole ligand features, which depend on the subunits, can be implemented in the final NCs, providing feedback for refined design, toward a priori materials design. Ligand libraries can be fundamental to enabling colloidal NCs as reliable luminophores and (photo)catalysts.