We report the direct growth of highly single crystalline rhenium trioxide (ReO3) nanorods on a tungsten (W) microwire electrode via the physical vapor transport process without any catalyst. In our growth mode, ReO3 nanocubes were initially formed on the surface of a tungsten (W) microwire electrode and further they were anisotropically grown along the [001] crystallographic direction. Furthermore, we performed the fundamental electrochemical experiments so that from cyclic voltammetric measurements, ReO3 nanorods on a W microwire exhibit a good capacitance and Nernstian behavior for a Fe(CN)(6)(3-)/Fe(CN)(6)(4-) redox couple in 1 M KNO3 aqueous solution, indicating a promising electrode material for electrochemical applications.