Nanofilms of complicated architecture based on VO₂ and containing chromium were synthesized by the molecular layering method. The study of electrophysical characteristics of vanadium dioxide nanocrystallites and of VO₂-containing chromium has shown that semiconductor-metal phase transitions appear in the ranges of 130-160 and 100-110 K, respectively. The introduction of a transition-element ion in the nanostructures based on VO ₂ affects the phase transition characteristics.