Interface physics is at the heart of organic photovoltaics (OPV). Here we reveal for the first time the actual charge generation mechanism in a low-band-gap polymer: fullerene blend as prototypical system for efficient OPV. We demonstrate that the photogenerated excitons dissociate into bound interfacial charge transfer states (CTS) and free charges in 20-50 fs, with a branching ratio that depends on the excess energy. Providing an excess energy, high energy singlet polymer states are excited, giving a direct hot electron transfer into the interfacial hot CTS* before internal energy dissipation occurs. This process ultimately leads to a higher fraction of free charges. Thanks to strong electronic coupling between high-energy-states and hot CTS, we demonstrate the opening of additional paths for charge generation that would otherwise be quenched by internal conversion to the lowest-lying states. Our results provide a new framework to understand charge generation in OPV system, suggesting that hot dissociation is a strategic option to enhance the photovoltaic conversion.