We present strategies to improve low open-circuit voltage (V <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">oc</sub> ) for ZnO-poly(3-hexylthiophene) (P3HT) photovoltaic devices, which are typically ≤0.4 V, but vary among different reports. One factor affecting V <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">oc</sub> variability is the ZnO bandgap (E <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">g</sub> ), which depends on detailed processing conditions. By decreasing the pyrolysis temperature of sol-gel ZnO films, we increased the ZnO E <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">g</sub> by 0.14 eV and V <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">oc</sub> of corresponding bilayer devices by 0.1 V. This is understood as increased donor-acceptor energy-level offset. Next, we demonstrate significant enhancement in V <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">oc</sub> by depositing conformal amorphous TiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> films at the surface of planar ZnO films and ZnO nanorod arrays using a spin-coating method. The TiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> coatings monotonically increased V <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">oc</sub> from 0.4 to 0.8 V for devices with increasing TiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> thicknesses from 0 to ≥50 Å. Dark current-voltage measurement reveals that the TiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> coating significantly decreases the reverse-bias current density, leading to an improvement in V <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">oc</sub> , in excellent agreement with predictions from the modified ideal diode equation. This is consistent with passivation of ZnO surface defects by TiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> . In short, by varying the solution processing conditions, we modify the bulk and interfacial properties of the metal oxide acceptor, thus leading to systematic improvement in open-circuit voltage.