Self-assembled three-dimensional (3D) hierarchical BiVO4 microspheres from nanoplates have been first synthesized by a facile malic acid-assisted hydrothermal route on a large scale. In the present hydrothermal system, malic acid played key roles in controlling the morphology and quality of the resultant products. The as-synthesized 3D hierarchical BiVO4 microspheres exhibited good photocatalytic activity in degradation of Rhodamine B (RhB) under Xe-lamp light irradiation.