A novel property of red phosphorus for visible light driven photocatalytic H-2 formation from water by photogenerated electrons has been discovered. The detection of hydroxyl radicals and results from photoconductivity measurements confirmed the photogeneration of electrons and holes. Theoretical calculations also indicated that the reduction of water by photogenerated electrons would be energetically possible. A P-type semiconductor behavior of red phosphorus was observed. Our findings may provide insights for developing phosphorus-based photocatalysts. (C) 2011 Elsevier B.V. All rights reserved.