Here we investigate the dynamic self-assembly pathway of ordered gold nanocrystal arrays during the self-assembly of gold nanocrystal micelles, with and without the presence of colloidal silica precursors, using grazing-incidence X-ray scattering performed at a synchrotron source. With silica precursors present, a lattice with rhombohedral symmetry is formed from the partial collapse of a face-centered cubic structure. In the absence of silica, a transient body-centered orthorhombic phase appears, which rapidly collapses into a glassy nanocrystal film. The appearance of face-centered and body-centered structures is consistent with a phase diagram for charged colloidal particles with assembly modulated via Coulomb screening.