The ability of conjugated polymers to function as electronic materials is dependent on the efficient transport of excitons along the polymer chain. Generally, the photophysics of the chromophore monomer dictate the excited state behavior of the corresponding conjugated polymers. Different molecular structures are examined to study the role of excited state lifetimes and molecular conformations on energy transfer. The incorporation of rigid, three-dimensional scaffolds, such as iptycenes and cyclophanes, can encourage an oblique packing of the chromophore units of a conjugated polymer, thus allowing the formation of electronically-coupled aggregates that retain high quantum yields of emission. Rigid iptycene scaffolds also act as excellent structural directors that encourage complete solvation of PPEs in a liquid crystal (LC) solvent. LC-PPE mixtures display both an enhanced conformational alignment of polymer chains and extended effective conjugation lengths relative to isotropic solutions, which leads to enhanced energy transfer. Facile exciton migration in poly(p-phenylene ethynylene)s (PPEs) allows energy absorbed over large areas to be funneled into traps created by the binding of analytes, resulting in signal amplification in sensory devices. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 476-498, 2011