In this work, a fast (0.5 h), green microwave-assisted synthesis of single crystalline Sb2Se3 nanowires was developed. For the first time we demonstrated a facile solvent-mediated process, whereby intriguing nanostructures including antimony selenide (Sb2Se3) nanowires and selenium (Se) microrods can be achieved by merely varying the volume ratio of ethylene glycol (EG) and H2O free from expensive chemical and additional surfactant. The achieved uniform Sb2Se3 nanowire is single crystalline along [001] growth direction with a diameter of 100 nm and a length up to tens of micrometers. When evaluated as an anode of lithium-ion battery, Sb2Se3 nanowire can deliver a high reversible capacity of 650.2 mAh g−1 at 100 mA g−1 and a capacity retention of 63.8% after long-term 1000 cycles at 1000 mA g−1, as well as superior rate capability (389.5 mAh g−1 at 2000 mA g−1). This easy solvent-mediated microwave synthesis approach exhibits its great universe and importance towards the fabrication of high-performance metal chalcogenide electrode materials for future low-cost, large-scale energy storage systems.