TiO2 nanostructures are being sought after as flexibly utilizable building blocks for the fabrication of the mesoporous thin-film photoelectrodes that are the heart of the third-generation photovoltaic devices, such as dye-sensitized solar cells (DSSCs), quantum-dot-sensitized solar cells (QDSSCs), and the recently promoted perovskite-type solar cells. Here, we report deliberate tailoring of TiO2 nanostructures for superior photovoltaic cells. Morphology engineering of TiO2 nanostructures is realized by designing synthetic protocols in which the precursor hydrolysis, crystal growth, and oligomer self-organization are precisely controlled. TiO2 nanostructures in forms varying from isolated nanocubes, nanorods, and cross-linked nanorods to complex hierarchical structures and shape-defined mesoporous micro-/nanostructures were successfully synthesized. The photoanodes made from the shape-defined mesoporous TiO2 microspheres and nanospindles presented superior performances, owing to the well-defined overall shapes and the inner ordered nanochannels, which allow not only a high amount of dye uptake, but also improved visible-light absorption. This study provides a new way to seek an optimal synthetic protocol to meet the required functionality of the nanomaterials.