Orthorhombic α-MoO3 is a potential anode material for lithium-ion batteries due to its high theoretical capacity of 1100 mAh g−1 and excellent structural stability. However, its intrinsic poor electronic conductivity and high volume expansion during the charge–discharge process impede it from achieving a high practical capacity. A novel composite of α-MoO3 nanobelts and single-walled carbon nanohorns (SWCNHs) is synthesized by a facile microwave hydrothermal technique and demonstrated as a high-performance anode material for lithium-ion batteries. The α-MoO3/SWCNH composite displays superior electrochemical properties (654 mAh g−1 at 1 C), excellent rate capability (275 mAh g−1 at 5 C), and outstanding cycle life (capacity retention of '99% after 3000 cycles at 1 C) without any cracking of the electrode. The presence of SWCNHs in the composite enhances the electrochemical properties of α-MoO3 by acting as a lithium storage material, electronic conductive medium, and buffer against pulverization. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim