We propose a new mechanism by which the common electrolyte additive guanidinium thiocyanate (GdmSCN) improves efficiency in dye-sensitized solar cells (DSSCs). We demonstrate that binding of Gdm(+) to TiO2 is weak and does not passivate recombination sites on the TiO2 surface as has been previously claimed. Instead, we show that Gdm(+) binds strongly to the N719 and D131 dyes and probably to many similar compounds. The binding of Gdm(+) competes with iodine binding to the same molecule, reducing the surface concentration of dye-I2 complexes. This in turn reduces the electron/iodine recombination rate constant, which increases the collection efficiency and thus the photocurrent. We further observe that GdmNO3 can increase efficiency more than the current Gdm(+) source, GdmSCN, at least in some DSSCs. Overall, the results point to an improved paradigm for DSSC operation and development. The TiO2/electrolyte surface has long been held to be the key interface in DSSCs. We now assert that the dye layer/electrolyte interaction is at least, and probably more, important.