In this paper, we present a novel, high-yield, and cost-effective hydrothermal method for the preparation of single crystal-like anatase TiO2 nanorods (NRs) with specific {101} exposed crystal planes and preferred [001] growth direction, which is governed by the "oriented attachment" mechanism. The successful synthesis of TiO2 NRs and fine tuning on their size and shape could be easily accomplished by adjusting the solvent compositions. The salient feature of these NRs, in lieu of traditional nanoparticles as building blocks of photoanodes in dye-sensitized solar cell (DSSC) system, rests with their significantly reduced grain boundaries. The electron diffusion and recombination kinetics have been critically compared for the first time with respect to the size and shape of the novel building blocks. A high efficiency of 8.87% has finally been achieved for DSSC based on long-thin NRs rather than short-thin or long-thick NRs, which possesses balanced optimizations on charge collection and light-harvesting properties.