Conventional descriptions of excitons in semiconducting polymers do not account for several important observations in polymer:fullerene photovoltaic blends, including the ultrafast time scale of charge photogeneration in phase separated blends and the intermediate role of delocalized charge transfer states. We investigate the nature of excitons in thin films of polymers and polymer:fullerene blends by using broadband ultrafast photoluminescence spectroscopy. Our technique enables us to resolve energetic relaxation, as well as the volume of excitons and population dynamics on ultrafast time scales. We resolve substantial high-energy emission from hot excitons prior to energetic relaxation, which occurs predominantly on a subpicosecond time scale. Consistent with quantum chemical calculations, ultrafast annihilation measurements show that excitons initially extend along a substantial chain length prior to localization induced by structural relaxation. Moreover, we see that hot excitons are initially highly mobile and the subsequent rapid decay in mobility is correlated with energetic relaxation. The relevance of these measurements to charge photogeneration is confirmed by our measurements in blends. We find that charge photogeneration occurs predominately via these delocalized hot exciton states in competition with relaxation and independently of temperature. As well as accounting for the ultrafast time scale of charge generation across large polymer phases, delocalized hot excitons may also account for the crucial requirement that primary charge pairs are well separated in efficient organic photovoltaic blends.