Nanoscale vanadium dioxide doped with chromium and iron is obtained via molecular layering method on the surface of a single-crystal silicon. The qualitative and quantitative composition of the samples is determined by photometry and magnetochemical analysis. The morphology is examined by AFM and SEM. Two independent methods (magnetic susceptibility and impedance spectroscopy) show the presence of the semiconductor-metal phase transition in the obtained structures in the range 100-125 K. The considerable influence of the alloying element content on the characteristics of the phase transition, including its temperature, is established.