As a transition metal oxide, VO2 has excellent optical and electrical properties and is widely used in many fields. The production of VO2 by the reduction of NH4VO3 and V2O5 will inevitably produce ammonia–nitrogen wastewater and NH3 emission during the production of NH4VO3 and V2O5, which will cause serious environmental pollution and will increase economic costs. The large-scale and low-cost synthesis of VO2 still faces great challenges. In this paper, VO2(B) was successfully prepared by a one-step hydrothermal method using NaVO3 as the vanadium source and CH3CH2OH as the reducing agent, and the optimal conditions for vanadium precipitation are as follows: vanadium concentration = 30 g/L, CH3CH2OH dosage = 20 % (percentage of solution volume), initial pH = 1, reaction temperature = 220 °C, reaction time = 12 h. The vanadium precipitation efficiency under the optimal conditions could reach 98.93 %, and the purity of VO2(B) could reach 98.59 %. The precipitation products were characterized by XRD, TG, FTIR, XPS, and SEM-EDS. The mechanism of VO2(B) preparation by ethanol reduction was proposed. This process is characterized by green, clean, and high efficiency. At the same time, the vanadium precipitation effect and vanadium precipitation products of various alcohols were studied to provide technical and theoretical support for the preparation of VO2(B).