The embodiments described herein relate generally to methods, compositions, articles, and devices associated with layer-by-layer assembly and/or functionalization of carbon-based nanostructures and related structures. In some embodiments, the present invention provides methods for forming an assembly of carbon-based nanostructures on a surface. The carbon-based nanostructure assembly may exhibit enhanced properties, such as improved arrangement of carbon-based nanostructures (e.g., carbon nanotubes) and/or enhanced electronic and/or ionic conductivity and/or other useful features. In some cases, improved properties may be observed due to the attachment of functional groups to the surfaces of carbon-based nanostructures. Using methods described herein, formation of carbon-based nanostructure assemblies may be controlled to produce structures with enhanced properties.