We demonstrate a new hierarchical self-assembly strategy for the formation of photonic arrays containing quantum dots (QDs), in which sequential self-assembly steps introduce organization on progressively longer length scales, ranging from the nanoscale to the microscale regimes. The first step in this approach is the self-assembly of diblock copolymers to form block ionomer reverse micelles (SA1); within each micelle core, a single CdS QD is synthesized to yield the hybrid building block BC-QD. Once SA1 is completed, the hydrophobic BD-QD building blocks are blended with amphiphilic block copolymer stabilizing chains in an organic solvent; water addition induces secondary self-assembly (SA2) to form quantum dot compound micelles (QDCMs). Finally, aqueous dispersions of QDCMs are slowly evaporated to induce the formation of three-dimensional (3D) close-packed arrays in a tertiary self-assembly step (SA3). The resulting hierarchical assemblies, consisting of a periodic array of hybrid spheres each containing multiple CdS QDs, exhibit the collective property of a photonic stop band, along with photoluminescence arising from the constituent QDs. A high degree of structural control is possible at each level of organization by judicious selection of experimental variables, allowing various parameters governing the collective optical properties, including QD size, nanoparticle spacing, and mesocale periodicity, to be independently tuned. The resulting control over optical properties via successive self-assembly steps should provide new opportunities for hierarchical materials for QD lasers and all-optical switching.