Large scale three-dimensional supercrystals were grown by controlling evaporation of truncate PbS nanocrystal (NC) dispersed hexane suspensions. Electron microscopy analysis confirmed the nature of single supercrystal with a face-centered cubic (fcc) lattice. Synchrotron small/wide angle scattering (SAXS/WAXS) images from three typical crystallographic projections allowed ultimate reconstruction of shape orientations of NCs at different crystallographic sites. Position exchange of distinctly oriented NCs between crystallographic sites produces two nondegeneration shape-related pseudo-polymorphs of superlattice that accordingly reduce symmetry from O-h to C-4h and C-2h with various facet-to-facet arrangements, respectively. In situ SAXS measurements of NC-assembled supercrystal and lead oleate and oleic acid upon pressurization provide additional insights into surface ligand density and the nature of ligand-NC interactions and resulting interface structure. These results allow for feasible evaluation of both NC shape and ligand conformation enabled effects that govern the formation and stability of truncate NC assemblies with various superlattice polymorphs and associated NC-ligand interactions in solvent-mediated assembled processes.