The surface chemistry of ZnO single crystals of (0001) and (1010) orientations and ZnO nanorods was studied using x-ray and ultraviolet photoelectron spectroscopies. Air drying and UV-ozone preparations were studied in particular as chemical treatments that could be applied to poly(3-hexylthiophene) (P3HT)-ZnO solar cells to enhance performance. The UV-ozone treatment showed negligible effect by photoelectron spectroscopy on the ZnO single crystal surfaces, but brought about electronic shifts consistent with increased upward band bending by similar to 0.25 eV on the ZnO nanorod surface. Modest interface dipoles of similar to 0.15 and similar to 0.25 eV were measured between P3HT and the (1010) and (0001) single crystal orientations, respectively, with the dipole moment pointing from ZnO to the P3HT layer. The sol-gel films showed evidence of forming a small interface dipole in the opposite direction, which illustrates the difference in surface chemistry between the solution-grown ZnO and the ZnO single crystals.