Important limitations in the application of light metal hydrides for hydrogen storage are slow kinetics and poor reversibility. To alleviate these problems doping and ball-milling are commonly applied, for NaAlH4 leading to particle sizes down to 150 nm. By wet-chemical synthesis we have prepared carbon nanofiber-supported NaAlH4 with discrete particle size ranges of 1-10 mu m, 19-30 nm, and 2-10 nm. The hydrogen desorption temperatures and activation energies decreased from 186 degrees C and 116 kJ(.)mol(-1) for the largest particles to 70 degrees C and 58 kJ(.)mol(-1) for the smallest particles. In addition, decreasing particle sizes lowered the pressures needed for reloading. This reported size-performance correlation for NaAlH4 may guide hydrogen storage research for a wide range of nanostructured light (metal) hydrides.