A study of cofacially arrayed π-systems is of particular importance for the design of functional materials for efficient long-range intra-chain charge transfer through the bulk semiconducting materials in the layers of photovoltaic devices. The effect of π-stacking between a pair of aromatic rings has been mainly studied in the form of cyclophanes, where aromatic rings are forced into a sandwich-like geometry, which extensively deforms the aromatic rings from planarity. The synthetic difficulties associated with the preparation of cyclophane-like structures has prevented the synthesis of many examples of their multi-layered analogues. Moreover, the few available multi-layered cyclophanes are not readily amenable to the structural modification required for the construction of D–spacer–A triads needed to explore mechanisms of electron and energy transfer. In this review, we recount how a detailed experimental and computational analysis of 1,3-diarylalkanes led to the design of a new class of cofacially arrayed polyfluorenes that retain their π-stacked structure. Thus, efficient synthetic strategies have been established for the ready preparation of monodisperse polyfluorenes with up to six π-stacked fluorenes, which afford ready access to D–spacer–A triads by linking donor and acceptor groups to the polyfluorene spacers via single methylenes. Detailed1H NMR spectroscopy, X-ray crystallography, electrochemistry, and He(I) photoelectron spectroscopy of F2–F6 have confirmed the rigid cofacial stacking of multiple fluorenes in F2–F6, despite the presence of rotatable C–C bonds. These polyfluorenes (F2–F6) form stable cation radicals in which a single hole is delocalized amongst the stacked fluorenes, as judged by the presence of intense charge-resonance transition in their optical spectra. Interestingly, these studies also discern that delocalization of a single cationic charge could occur over multiple fluorene rings in F2–F6, while the exciton is likely localized only onto two fluorenes in F2–F6. Facile synthesis of the D–spacer–A triads allowed us to demonstrate that efficient triplet energy transfer can occur through π-stacked polyfluorenes; the mechanism of energy transfer crosses over from tunneling to hopping with increasing number of fluorenes in the polyfluorene spacer. We suggest that the development of rigidly held π-stacked polyfluorenes, described herein, with well-defined redox and optoelectronic properties provides an ideal scaffold for the study of electron and energy transfer in D-spacer-A triads, where theFnspacers serve as models for cofacially stacked π-systems.