Nanoparticle assembly has been proposed as an ideal means to program the hierarchical organization of a material by using a selection of nanoscale components to build the entire material from the bottom up. Multiscale structural control is highly desirable because chemical composition, nanoscale ordering, microstructure and macroscopic form all affect physical properties(1,2). However, the chemical interactions that typically dictate nanoparticle ordering(3-5) do not inherently provide any means to manipulate structure at larger length scales(6-9). Nanoparticle-based materials development therefore requires processing strategies to tailor micro- and macrostructure without sacrificing their self-assembled nanoscale arrangements. Here we demonstrate methods to rapidly assemble gram-scale quantities of faceted nanoparticle superlattice crystallites that can be further shaped into macroscopic objects in a manner analogous to the sintering of bulk solids. The key advance of this method is that the chemical interactions that govern nanoparticle assembly remain active during the subsequent processing steps, which enables the local nanoscale ordering of the particles to be preserved as the macroscopic materials are formed. The nano- and microstructure of the bulk solids can be tuned as a function of the size, chemical makeup and crystallographic symmetry of the superlattice crystallites, and the micro- and macrostructures can be controlled via subsequent processing steps. This work therefore provides a versatile method to simultaneously control structural organization across the molecular to macroscopic length scales.