The high-energy milling of the V 2 O 5 -Na 2 SO 3 mixture in the range of 5 -100 min leads to a synthesis of monoclinic VO 2 . The starting and minimum (at 220 °C) values of electric resistance R of the 100 min milled and pressed VO 2 -Na 2 SO 4 mixture were 13.9 MΩ and 91.5 kΩ, respectively. The subsequent washing of the as-milled powder partially leads to the development of VO 2 nanostructures with tube-like, sheet-like and rod-like morphology, besides VO 2 (B) belt-like morphology, depending on the milling times.