Li3VO4 (LVO) is a promising insertion-type anode material for lithium ion batteries (LIBs) while its electrochemical performance in magnesium ion batteries (MIBs) is rarely reported. Here, mesoporous LVO/Carbon (LVO/C) hollow spheres are synthesized by a facile spray-drying method and their electrochemical performance as Mg2+ insertion-host material is investigated for the first time. Galvanostatic charge-discharge results of LVO/C show no obvious platform in the potential range of 0.5∼2.5V vs. Mg2+/Mg. The LVO/C delivers a high discharge capacity of 318mAhg−1 at first cycle and exhibits good cycle performance. The electrochemical intercalation process is proved by element mapping, ex-situ X-ray Powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. Our results show that LVO is a promising anode material for MIBs.