[en] Vesicular lithium vanadium phosphate/carbon hollow mesoporous microspheres were fabricated using a facile polyvinylpyrrolidone-assisted aerosol-spray-assisted method and subsequent heat-treatment. While changing the content of polyvinylpyrrolidone, we found that carbon content was adjustable on the surface of lithium vanadium phosphate. By optimizing the carbon content among the composites, the electrochemical performance can be enhanced significantly. The results of electrochemical performance tests suggested that the samples exhibited good cycle performance and high discharge capability in the voltages between 3.0–4.8 V. The observed excellent electrochemical performances could be attributed to the proper content of carbon coating and the vesicular hollow mesoporous microsphere structure, increasing the transmission rate of lithium ions and reducing the structural change during charging and discharging effectively. .