We report a hydrothermal synthesis method for MgO shell coatings directly onto the surface of ZnO nanowire arrays. The entire process can be carried out below 100 °C. The MgO shells are produced by the addition of 10 mM magnesium nitrate with 0.2 M sodium hydroxide in water, resulting in a shell thickness of up to 8 nm, verified by high resolution transmission electron microscopy. The viability of the MgO layer as a functional element of optoelectronic devices was tested on solid-state organic hole-transporter based dye-sensitized solar cells. Incorporation of the MgO shell into the solar cell resulted in substantive efficiency improvements of over 400% in comparison to the pristine ZnO nanowire based photovoltaics, indicating that electrons can efficiently tunnel through the 'insulating' MgO shell.