Charge separation is at the heart of solar energy applications, and efficient materials require fast photoinduced electron transfer (ET) and slow charge recombination (CR). Using time-dependent self-consistent charge density functional tight-binding theory combined with nonadiabatic (NA) molecular dynamics, we report a detailed analysis of ET and CR in hybrids composed of photoactive covalent organic polyhedra (COP) and encapsulated fullerenes. The ET occurs on a subpicosecond time scale and accelerates with increasing fullerene diameter, C