Herein, we demonstrate the shape- and size-selective growth of ZnO nanostructures on indium tin oxide-coated glass substrates by using a microwave-assisted chemical bath deposition method. By systematically controlling the deposition parameters, it is possible to produce shape- and size-selective nanostructures with high alignment and uniformity. Specifically, the pH of the bath can be used to control the shape of rods from bundled structures to tapered and flat tips. Furthermore, the deposition temperature can be used to control the size of the ZnO array from 770 to 125 nm. The prepared rods were active catalysts in the degradation of methylene blue under UV radiation, and exhibited size-dependent activity.