We report the synthesis of ruthenium dioxide (RuO2) nanostructures by thermal evaporation of RuO2 powder. RuO2 nanostructures of different shapes were synthesized at various concentration, flow rate, and pressure of oxygen. At a constant pressure of 3 torr of flowing oxygen, polygonal prism-like RuO2 nanorods with flat tips were grown at an O-2 flow rate of 100 sccm; club-shaped nanorods with obelisk tip were formed at 300 and 600 sccm, and hollow rods with square tip were formed at 1800 sccm. A mixture of O-2 and Ar at a total flow rate of 600 sccm led to the formation of short club-shaped nanorods indicating the suppression effect of Ar on the growth of nanorods. The pressure also had a significant effect on the formation of RuO2 nanostructures, at a fixed flow rate of 600 sccm of O-2, a pressure of 3 torr resulted in the growth of club-shaped RuO2 nanorods, while high pressures of 380 and 760 torr resulted in the formation of both linear club-shaped and pine tree-like hierarchical RuO2 nanorods. X-ray diffraction and transmission electron microscopy analysis indicated the formation of tetragonal phase of RuO2 with high crystallinity. A density functional calculation on RuO2, RuO3, and RuO4 was performed to help to explain the experimental results.