Electron recombination is one of the major loss factors in dye-sensitized solar cells (DSC), especially, with single electron outer sphere redox shuttle electrolyte. Insulating sub-nanometer oxide tunneling layers deposited by atomic layer deposition (ALD) are known to block the electron recombination, thereby leading to an increase in the open-circuit potential and the collection efficiency of the solar cell. A general perception in the DSC community is that any insulating oxide layer can block the recombination. However, in this work, it is unraveled that the insulating property of oxides alone is not sufficient. In addition, the properties such as the conduction band position and the oxidation state of the insulating oxide, the electronic structural modification induced to the underlying TiO2 mesoporous film, modification of surface charges (isoelectric point) and charge of the electrolyte species have to be considered. A complete photovoltaic study is done by depositing different cycles (by ALD) of four different insulating oxides (Ga2O 3, ZrO2, Nb2O5, and Ta 2O5) and their recombination characteristics, surface electronic properties, transport rate, and injection dynamics are investigated with a standard organic dye and Co2+/Co3+ redox mediator. A comparison is made with the conventional iodide/triiodide electrolyte. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.