Liquid-phase processing and colloidal self-assembly will be critical to the successful implementation of nanotechnology in the next generation of materials and devices. A key hurdle to realizing this will be the development of efficient methods to purify nanomaterials composed of a variety of shapes, including nanocrystals, nanotubes, and nanoplates. Although density-gradient ultracentrifugation (DGU) has long been appreciated as a valuable tool for separating biological macromolecules and components, the method has recently emerged as an effective way to purify colloidal nanoparticles by size and optical and electronic properties. In this feature article, we review our recent contributions to this growing field, with an emphasis on some of the implications that our results have for interfaces and materials. Through transient or isopycnic DGU performed in both aqueous and organic environments, we demonstrate some explicit examples of how the mechanical, electronic, and optical properties of thin films assembled from two specific colloidal nanomaterials-single-walled carbon nanotubes and silicon nanocrystals-can be modified in response to fractionation.