<p>Spin-active dopants offer a powerful yet largely unexplored route for controlling interfacial redox chemistry in quantum-confined semiconductors. Here we show that manganese doping in cadmium selenide quantum dots enables an ultrafast spin-exchange-mediated electron-transfer pathway that allows methyl viologen reduction even when conventional band-edge energetics are unfavorable for charge transfer. Femtosecond transient absorption spectroscopy reveals that manganese dopants accelerate electron-transfer dynamics by more than an order of magnitude while opening a hot-exciton reduction channel in which a manganese ion captures a photoexcited exciton prior to phonon-assisted cooling. Subsequent spin-flip relaxation of the excited manganese ion drives charge separation and reduction of a molecular acceptor. This mechanism operates efficiently across resonant and off-resonant (energy-uphill and downhill) regimes, identifying spin-exchange coupling—rather than band alignment—as the dominant factor governing electron-transfer rates and efficiencies. These findings establish magnetic doping as a viable strategy for harvesting hot carriers and enabling energetically demanding photocatalytic transformations.</p>