Vanadium dioxide thin films have been grown from vanadium tetrakis (t-butoxide) by the sol-gel process. A new method for the synthesis of the vanadium precursor was also developed. Films were deposited by dipcoating glass slides from an isopropanol solution, followed by post-deposition annealing of the films at 600°C under nitrogen. The properties of these films, to a high degree, were a function of crystalline boundaries and crystalline grain size. These gel-derived VO2 films undergo a reversible semiconductor-to-metal phase transition near 72°C, exhibiting characteristic resistive and spectral switching comparable with near stoichiometric VO2 films prepared on non-crystalline substrates by other techniques. Films were doped with hexavalent transition metal oxides to demonstrate lowering of the transition of the transition temperature.