This study represents a facile but efficient glycothermal method for synthesis of vanadium dioxide, VO₂(B) nanoparticles with various geometries from spheres to rods, flakes or their agglomeration structures, by controlling reaction conditions (e.g., vanadium resources, reducing agents and surfactants). The as-prepared VO₂(B) nanoparticles were characterized in microstructure and composition, and also examined in terms of gas sensing performance. It was found that the VO₂(B) nanoparticles exhibit a good sensitivity towards alcohols (ethanol, isopropanol, and butanol) and acetone at the optimised operating temperature of 300 °C. The gas sensing performance was further compared with other vanadium oxides investigated previously, such as V₂O, NaV₃O. The plausible gas sensing mechanism of the as-prepared nanoparticles was discussed in detail. This study would expand the family of vanadium oxides that can be made as potential sensors for applications in detecting environmental safety and human health.