VO₂ (B), VO₂ (A) and VO₂ (M) polymorphs were obtained by energy efficient semi-industrial hydrothermal process. Synthesis of thermochromic VO₂ (M) was performed in two steps and included thermal treatment in an inert atmosphere. The crystallographic peculiarities were observed by powder X-ray diffraction study. Scanning electron microscopy and specific surface area estimation showed the influence of recrystallization on the particles size and shape. The technique of VO₂ surface modification with electrically conductive polymer (polyaniline) was developed and proved by infrared spectroscopy. The impact of the polymer on the composite properties was investigated in case of three different crystal phases of VO₂ with different functionality. Vibrating-sample magnetometry, impedance spectroscopy, cyclic voltammetry and room condition modelling showed that polyaniline surface leads to competitive interactions but doesn't ruin optical switching abilities of VO₂ (M). Polyethylene glycol as electrically nonconductive matrix demonstrated the difference in electrical conductivity between VO₂ phases while conductive polyaniline eliminated them.