The advent and refinement of chemical techniques to produce uniform collections of colloidal nanocrystals in recent years has made accessible a wide range of nanocrystal materials, shapes, and sizes, offering a fertile testbed for developing an understanding of nanoscale crystallization. Elucidating the role of nanocrystal surfaces in promoting self-assembly of superlattice phases unanticipated by hard-shape packing models has been the focus of my graduate work. Chapter One provides a practical overview of the experimental approaches to prepare and characterize colloidal nanocrystals and self-assembled nanocrystal superlattices. Chapter Two discusses colloidal nanocrystal surfaces including atomic composition, chemical reactivity, and influence over electronic structure. Chapter Three provides an overview of nanocrystal self-assembly including interparticle potentials and predicted phase behavior for hard and soft shapes. Chapter Four describes the preparation of tetrahedrally-shaped CdSe nanocrystals and their self-assembly into an unexpected superlattice structure. Chapter Five presents a selection of electron microscopy images of superlattices comprised of nearly spherical nanocrystals. Chapter Six describes the application of image analysis techniques to elucidate ligand shell deformability of spherical nanocrystals and resulting implications for entropy-driven crystallization of soft objects. Chapter Seven analyzes the role of PbS surface ligand desorption in determining binary phase behavior with Au nanocrystals. Chapter Eight describes the implications of the ideas presented in this thesis, places them in the context of recent work by others in the field, and offers an outlook towards promising directions for future research. Together, the ideas contained herein aim to provide the conceptual foundation necessary to exploit nanocrystal self-assembly for the rational design of next-generation functional solids.