The photochemistry of oriented rutile surfaces has been examined using the photoreduction of Ag+ to Ag metal from an aqueous solution onto the TiO2 surfaces. The photochemical reaction rates and quantum yields of rutile films were found to be a function of the orientation of the rutile surface. The (100) and (110) rutile orientations have lower photoreduction rates than the (101), (111), and (001). This dependence of the photochemical reaction rates on film surface orientation is observed over a range of light intensities, illumination wavelengths, and film thicknesses. Atomic force microscopy has been used to characterize the morphologies of the film surfaces and the photoreduced Ag at these surfaces. Several properties of rutile! such as the surface morphology, surface chemistry, space charge phenomena, and charge transport, are discussed in relation to their possible contributions to the orientation dependence of the photochemistry on the rutile films.