Recent studies have shown that efficient free carrier (FC) generation with a small voltage loss can be achieved in organic solar cells (OSCs); however, the photophysical insights underpinning this remain unclear. I will talk about the mechanisms underlying the FC generation in a state-of-the-art OSC consisting of PM6 and Y6 as an electron donor and acceptor, respectively, wherein the energy offset between the lowest excited singlet state and the charge transfer state is as small as ~0.1 eV. In this study, transient absorption spectroscopy was used to track the time evolution of electroabsorption caused by electron–hole pairs generated at donor/acceptor interfaces. After hole transfer from Y6 to PM6, slow yet efficient spatial charge dissociation on a time scale of picoseconds was observed. Based on temperature dependence measurements, it is found that this slow yet efficient FC generation is driven by downhill energy relaxation of charges through the energy cascade generated near the interfaces.