We demonstrate that nanosize silicon (~10 nm diameter) reacts with water to generate hydrogen 1000 times faster than bulk silicon, 100 times faster than previously reported Si structures, and 6 times faster than competing metal formulations. The H(2) production rate using 10 nm Si is 150 times that obtained using 100 nm particles, dramatically exceeding the expected effect of increased surface to volume ratio. We attribute this to a change in the etching dynamics at the nanoscale from anisotropic etching of larger silicon to effectively isotropic etching of 10 nm silicon. These results imply that nanosilicon could provide a practical approach for on-demand hydrogen production without addition of heat, light, or electrical energy.