As a crucial mechanism of non-classical crystallization, the oriented attachment (OA) growth of nanocrystals is of great interest in nanoscience and materials science. The OA process occurring in aqueous solution with chemical reagents has been reported many times, but there are limited studies reporting the OA growth in pure water. In this work, we report the temperature-dependent OA growth of cuprous oxide (Cu2O) nanowires in pure water through a reagent-free electrophoretic method. Our experiments demonstrate that Cu2O quantum dots randomly coalesced to form polycrystalline nanowires at room temperature, while they form monocrystalline nanowires at higher temperatures by the OA mechanism. DFT modeling and computations indicate that the water coverage on the Cu2O nanoparticles could affect the particle attachment mechanisms. This study sheds light on the understanding of the effects of water molecules on the OA mechanism and shows new approaches for better controllable non-classical crystallization in pure water.