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A blocking effect on the approach of electron acceptors into a dye/TiO2 electrode in a dye-sensitized solar cell was confirmed by the observation of charge dynamics at the interface when an alkyl-functionalized dye was used. It was found that the density of the adsorbed MK-2 on the TiO2 surface affected the ionic motion in an electrolyte at the interface, and that electron–electrolyte recombination was suppressed with a high density of adsorbed MK-2 molecules, causing prevention of the approach of the redox ions.