Silver nanocrystals are ideal building blocks for plasmonic materials that exhibit a wide range of unique and potentially useful optical phenomena. Individual nanocrystals display distinct optical scattering spectra and can be assembled into hierarchical structures that couple strongly to external electromagnetic fields. This coupling, which is mediated by surface plasmons, depends on their shape and arrangement. Here we demonstrate the bottom-up assembly of polyhedral silver nanocrystals into macroscopic two-dimensional superlattices using the Langmuir-Blodgett technique. Our ability to control interparticle spacing, density, and packing symmetry allows for tunability of the optical response over the entire visible range. This assembly strategy offers a new, practical approach to making novel plasmonic materials for application in spectroscopic sensors, sub-wavelength optics, and integrated devices that utilize field enhancement effects.