Recently, the performance of organic solar cells has been markedly improved benefiting from the development of nonfullerene acceptors (NFAs) with acceptor-donor-acceptor structures. Arising from the intermolecular electronic interactions between the electron donating and accepting units, intramoiety and interfacial delocalized excitations make a substantial contribution to the photocurrent generation. In this Perspective, we discuss recent studies on the excited-state dynamics responsible for the working mechanism in NFA-based organic solar cells and emphasize the dynamics of delocalized excitations in charge generation and recombination processes. The intramoiety delocalized excitations in NFAs enable charge separation without forming interfacial charge-transfer excitons first, allowing efficient photocharge generation in planar heterojunctions with reduced interfacial energy loss. We suggest a few research directions in elucidating the performance-limited processes toward the further optimization of NFA-based devices.