In this work, rattle-type ball-in-ball V2O5 hollow microspheres are controllably synthesized with the assistance of carbon colloidal spheres as hard templates. Carbon spheres@vanadium-precursor (CS@V) core–shell composite microspheres are first prepared through a one-step solvothermal method. The composition of solvent for the solvothermal synthesis has great influence on the morphology and structure of the vanadium-precursor shells. V2O5 hollow microspheres with various shell architectures can be obtained after removing the carbon microspheres by calcination in air. Moreover, the interior hollow shell can be tailored by varying the temperature ramping rate and calcination temperature. The rattle-type V2O5 hollow microspheres are evaluated as a cathode material for lithium-ion batteries, which manifest high specific discharge capacity, good cycling stability and rate capability.