Time-resolved optical spectroscopies reveal multielectron transfer from the biexcitonic state of a CdS quantum dot to an adsorbed tetracationic compound cyclobis(4,4'-(1,4-phenylene) bipyridin-1-ium-1,4-phenylene-bis(methylene)) (ExBox(4+)) to form both the ExBox(3+•) and the doubly reduced ExBox(2(+•)) states from a single laser pulse. Electron transfer in the single-exciton regime occurs in 1 ps. At higher excitation powers the second electron transfer takes ∼5 ps, which leads to a mixture of redox states of the acceptor ligand. The doubly reduced ExBox(2(+•)) state has a lifetime of ∼10 ns, while CdS(+•):ExBox(3+•) recombines with multiple time constants, the longest of which is ∼300 μs. The long-lived charge separation and ability to accumulate multiple charges on ExBox(4+) demonstrate the potential of the CdS:ExBox(4+) complex to serve as a platform for two-electron photocatalysis.