Molecular photoelectrochemical (PEC) devices are hampered by electron–hole recombination after photoinduced electron transfer (PET), causing losses in power conversion efficiency (PCE). Inspired by natural photosynthesis, we demonstrate the use of molecular machinery as a strategy to inhibit recombination, through organization of molecular components and unbinding of the final electron acceptor after reduction. We show that preorganization of the macrocyclic 3-NDI-ring electron acceptor to the PSTATION dye forming the PSTATION:3-NDI-ring pseudorotaxane, enables a “ring launching” event, upon PET from PSTATION to 3-NDI-ring releasing 3-NDI-ring•−. Implementing PSTATION:3-NDI-ring into p-type dye-sensitized solar cells (p-DSSCs) revealed a fivefold increase in PCE compared to benchmark dye P1, unable to facilitate pseudorotaxane formation. This active repulsion of anionic 3-NDI-ring•− with concomitant reformation PSTATION:3-NDI-ring circumvents recombination at semiconductor–dye interface, affording a twofold enhancement in hole lifetime. We envision this concept of supramolecular-directed charge-propagation will encourage further integration of molecular machinery into PEC devices.