Hybrid materials with hierarchical nanostructures are of great interest for their advanced functions. However, the effect of the formation of hierarchical nanostructures on properties is not well understood. Here, through combining dissipative particle dynamics simulation and the finite‐difference time‐domain method, the optical properties of hierarchically ordered nanostructures formed by mixtures of A(BC)n multiblock copolymers and nanoparticles (NPs) are investigated. A series of hierarchically ordered nanostructures with multiple small‐length‐scale hybrid domains are obtained from the self‐assembly of A(BC)n/NP. An increase and blueshift in optical absorption are observed when the number of small‐length‐scale hybrid domains increases. The small‐length‐scale hybrid domains enhance light scattering, which consequently contributes to the improved optical performance. These findings can yield guidelines for designing hierarchically ordered functional nanocomposites with light‐harvesting characteristics. Hierarchically ordered nanostructures with multiple small‐length‐scale hybrid domains are formed by mixtures of multiblock copolymers and nanoparticles. Theoretical simulations reveal that the hierarchical hybrid nanostructures give rise to an increase and blueshift in optical absorption.