Metallic bismuth crystal is one important and interesting semimetal that has attracted great attention owing to its unique thermal and electrical properties. Herein, we report a facile, green, cost-effective and sustainable solvothermal process using ethanol, glycol, isopropanol, phenylcarbinol as solvent and commercial Bi2O3 as the starting material to produce high-purity metallic Bi with tunable morphologies on large scale. It is found that all alcohols are capable of reducing Bi2O3 to Bi and the reducibility of glycol is proved to be the strongest. The highest purity of the resultant Bi is calculated to be 99.74%. What's more, the morphology of final Bi particles is controllable by adding various types and concentrations of additives. As a consequence, our work lays the root for the large scale solvothermal production of high-purity Bi particles with various regular morphologies. (C) 2017 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.