A novel ZnO-FTO heterostructure nanotube array was produced by combining a chemical solution process with oxygen-plasma etching. In this approach, presynthesized ZnO nanorod arrays act as templates, and FTO nanoparticles are deposited onto the ZnO nanorods by a simple spray pyrolysis method. X-ray photoelectron spectroscopy analysis demonstrated that the oxygen-plasma treatment decreased the O(2-)/OH(-) concentration ratio, resulting in dissociation of the Zn-O bonds and the outward diffusion of Zn cations to form an interior hollow, which is related to the formation of the hydroxyl functional group, Sn-OH, at the FTO surface. An etching evolution mechanism of the ZnO-FTO nanotubes via oxygen plasma was tentatively proposed in this study. Time-dependent photocurrent (I-T) measurements under ON-OFF cycles of UV illumination confirm that the 20-min etched sample exhibits a rectified photoresponse characteristic and a dark current increased by about 3 orders of magnitude over that of the unetched sample, which is attributed to the increased carrier concentration created at the surface conductive layer. This investigation offers an alternative selective etching method to lay the framework for nanoscale three-dimensional electrodes for solar-cell applications.