BiVO4 as one of the promising visible-light-driven photocatalysts attracted considerable research on morphology and composition control. In this work, a modified carbonaceous spheres sacrificial template growth technique are developed to build up multi-shell hollow spheres of the heterostructured Bi-V-O. By treating the carbonaceous spheres with NaOH aqueous, the simultaneous adsorption of Bi3+. and VO3- are achieved successfully, and through the precisely controlled calcination, the nanoparticles of BiVO4 and Bi4V2O11 are crystallized and interconnected into the Bi-V-O heterostructured multi-shell hollow spheres. These Bi-V-O hollow spheres demonstrate a high visible-light-driven photocatalytic activity towards the decomposition of Methylene blue, and the double-shell one with the highest Bi4V2O11 content shows the best photocatalytic activity. The high photocatalytic activity may due to the effective utilization of visible light induced by multiple reflections of their special multi-shell hollow spheres. The heterostructure between BiVO4 and Bi4V2O11 may also make a contribution to the enhanced photocatalytic activity. (C) 2016 Elsevier Ltd. All rights reserved.