Colloidal nanocrystals can combine the benefits of inorganic semiconductors with size-tunable electronic structure and inexpensive solution-based device fabrication. Single- and multicomponent nanocrystal assemblies, also known as superlattices, provide a powerful general platform for designing two- and three-dimensional solids with tailored electronic, magnetic, and optical properties. Such assemblies built of “designer atoms” can be considered as a novel type of condensed matter, whose behavior depends both on the properties of individual building blocks and on the interactions between them. Efficient charge transport is crucial for applications of nanocrystal-based materials in various electronic and optoelectronic devices. For a long time, nanocrystals were considered poor electronic conductors. To facilitate charge transport, we developed novel surface chemistry using all-inorganic ligands, namely metal chalcogenide complexes that transformed colloidal nanomaterials into a very competitive class of solution-processed semiconductors for electronic, thermoelectric, and photovoltaic applications.