Crystallized and fluorinated nanoporous Ta(2)O(5) spheres were prepared by a combination of co-precipitation and hydrothermal methods in a NH(4)F-containing water solution. The as-prepared porous spheres, with a pore-size of around 7 nm and a large specific surface area of 132 m(2) g(-1), show superior photocatalytic hydrogen production activity over P25 and commercial-Ta(2)O(5).