Dendronized block copolymers were synthesized by ruthenium-mediated ring-opening methathesis polymerization of exo-norbomene functionalized dendrimer monomers, and their self-assembly to dielectric mirrors was investigated. The rigid-rod main-chain conformation of these polymers drastically lowers the energetic barrier for reorganization, enabling their rapid self-assembly to long-range, highly ordered nanostructures. The high fidelity of these dielectric mirrors is attributed to the uniform polymer architecture achieved from the construction of discrete dendritic repeat units. These materials exhibit light-reflecting properties due to the multilayer architecture, presenting an attractive bottom-up approach to efficient dielectric mirrors with narrow band gaps. The wavelength of reflectance scales linearly with block-copolymer molecular weight, ranging from the ultraviolet, through the visible, to the near-infrared. This allows for the modulation of photonic properties through synthetic control of the polymer molecular weight. This work represents a significant advancement in closing the gap between the precision obtained from top-down and bottom-up approaches.