Multifunctional Bi2O3 porous nanospheres (PNs) with tunable size have been successfully synthesized via a facile solvothermal method. The obtained Bi2O3 porous nanospheres demonstrate outstanding performance in visible-light-driven photocatalysis for Cr(VI) and organic dye removal, inactivation of Gram-negative and Gram-positive bacteria, as well as template-synthesis for fabrication of bismuth-related hollow nanostructures.