The mechanism by which the adsorbent guanidinium affects the open-circuit photovoltage of dye-sensitized TiO2 nanocrystalline solar cells was investigated. The influence of the guanidinium cation on the rate of recombination and band-edge movement was measured by transient photovoltage. When guanidinium is present in the electrolyte recombination becomes slower by a factor of about 20. At the same time, the adsorbent causes the band edges to move downward, toward positive electrochemical potentials, by 100 mV. The collective effect of both a downward shift of the band edges and slower recombination, owing to the presence of guanidinium, results in an overall improvement in the open-circuit photovoltage.