Despite the promise of quantum dots (QDs) as a light-absorbing material to replace the dye in dye-sensitized solar cells, quantum dot-sensitized solar cell (QDSSC) efficiencies remain low, due in part to high rates of recombination. In this article, we demonstrate that ultrathin recombination barrier layers of Al2O3 deposited by atomic layer deposition can improve the performance of cadmium sulfide (CdS) quantum dot-sensitized solar cells with spiro-OMeTAD as the solid-state hole transport material. We explored depositing the Al2O3 barrier layers either before or after the QDs, resulting in TiO2/Al2O3/QD and TiO 2/QD/Al2O3 configurations. The effects of barrier layer configuration and thickness were tracked through current-voltage measurements of device performance and transient photovoltage measurements of electron lifetimes. The Al2O3 layers were found to suppress dark current and increase electron lifetimes with increasing Al 2O3 thickness in both configurations. For thin barrier layers, gains in open-circuit voltage and concomitant increases in efficiency were observed, although at greater thicknesses, losses in photocurrent caused net decreases in efficiency. A close comparison of the electron lifetimes in TiO2 in the TiO2/Al2O3/QD and TiO2/QD/Al2O3 configurations suggests that electron transfer from TiO2 to spiro-OMeTAD is a major source of recombination in ss-QDSSCs, though recombination of TiO2 electrons with oxidized QDs can also limit electron lifetimes, particularly if the regeneration of oxidized QDs is hindered by a too-thick coating of the barrier layer. © 2013 American Chemical Society.