This presentation will highlight two recent projects from my laboratory in which we have 1) synthesized new electron accepting materials based on cyclopentafused-polycyclic aromatic hydrocarbons (CP-PAHs) and 2) created highly ordered polymer nanostructures via polychromophore architectures. In the first part of the talk, both small-molecule and polymeric electron acceptors that incorporate CP-PAH scaffolds will be described. Our synthetic strategy utilizes scalable processes to create halogenated CP-PAHs that can participate in a variety of palladium-catalyzed coupling chemistries. This approach allows easy modulation of the frontier orbital energies and thus provides access to tunable materials. In the second part of the talk, I will show how the chromophore length in a conjugated polymer composed of both rigid and flexible segments directly influences the anisotropy at the single polymer level. Our efforts to translate the packing order from the single polymer chain to polymer aggregates and films will be described.