Modified carbonaceous spheres sacrificial template approach. Controlling adsorption quantity of Bi3+ and VO3− ions in the carbonaceous microsphere templates and the heating process. Heterostructured Bi–V–O multi-shell hollow spheres. Effective separation of photogenerated electrons and holes as well as the effective utilization of visible light. Enhanced visible-light-driven photocatalytic activity towards the photodegradation of Methylene blue.