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Vertically aligned and well-separated single-crystal TiO2 NW arrays with a length of up to ∼10 μm were synthesized via a simple solvothermal method. The charge transport in these NWs is over 100 times faster than that of nanoparticle films and remarkably exhibits length-independence., Long, well-separated single crystal TiO2 nanowire (NW) arrays with rapid charge transport properties hold great promise in photoelectrochemical and energy storage devices. Synthesis variations to increase the NWs length generally result in the widening of the NWs and fusion at their roots which, in turn, increases the structural disorder and slows charge transport. As such, well-separated single-crystal TiO2 NW arrays with rapid charge transport properties have been limited to lengths of about 3–4 μm. In this work, by adjusting the HCl/DI-water ratio and adding specific organic ligands to the reaction solution that slow the lateral growth rate we achieve well-separated single-crystal rutile TiO2 NW arrays with a length of ∼10 μm and an aspect ratio of approximately 100. The charge transport is 100 times faster than that of nanoparticle films and remarkably exhibits length-independence, a behavior that can be attributed to the well-separated architecture. The synthesis strategy can be extended to the fabrication of other well-separated metal oxide NW arrays and represents an important tool in achieving high performance photoelectrochemical and electrical energy storage devices.