In this feature article, we review and examine evidence that the primary photoexcited species in conjugated polymers is considerably delocalized. Localization occurs via a series of complex relaxation mechanisms on the <200 femtosecond time scale. We show that short-lived delocalization in the neutral excited state and charge separated state of bulk heterojunction blends might play an essential role in ensuring efficient formation of free charge carriers for photovoltaic applications. Finally, the additional parameter of intramolecular charge transfer character in the excited state of more recently developed donor–acceptor copolymers is discussed. Both delocalization and partial charge transfer reduce the binding of the electron and hole in photoexcited organic semiconductors and can help to overcome the bottleneck to macroscopic current generation in polymer solar cells.