-The sol-gel science and technology demonstrate an intense development over past few decades accompanied by important applications in electronics. The sol-gel technology represents a typical example of nanotechnology, since the gel products are actually nanocomposites or may contain nanoparticles. That is why the sol-gel science plays a crucial role in the R&D of contemporary nanotechnology for the fabrication of novel materials with new functional properties. In this paper we present an overview of our previous results on the properties of vanadium oxide gel structures, as well as report some recent findings in this area. Electrical and optical (including electrochromic effect) properties, influence of doping with tungsten and hydrogen, electrical switching. Moreover, the properties of vanadium oxide micro-and nanofibers are systematically described and discussed. Applied potentialities of the described phenomena for micro-and optoelectronics (electrochromic devices, sensors, electronic switches, etc) are also discussed.Index Terms -Transition metal oxides, sol-gel, vanadium oxide, metal-insulator transition, electrochromic effect. 1