We report a novel hierarchically organized superstructure emerging from an exquisite association of inorganic crystals, organic polymers, and dyes. The resultant K2SO4/poly(acrylic acid) composite includes five different tiers from the nanoscopic to the macroscopic. An additional new tier leading to functionality is formed by the incorporation of organic dyes that are organized in a nanospace. The emergent superstructure and properties are designed through changes in polymer concentration. The multiple roles of the polymer realize the generation of the architecture at each size scale. This model approach should be widely applicable to other systems, allowing for the preparation of innovative materials by an appropriate combination of crystals, polymers, and functional molecules.