Direct electroless nickel plating on n-Si(100)wafers in alkaline solutions was demonstrated without any activation procedure in advance, the effect of pH and temperature of the solutions on size of metal particles in deposits was examined, and also the element contents of deposits were analyzed by energy disperse spectroscopy (EDS). The results indicated that the size of metal particles increases with increasing temperature or decreasing pH. The possible mechanism of nickel deposition on n-Si(100) was discussed in terms of semiconductor electrochemistry, and the formation of nickel seed crystal on Si was mainly attributed to the generation of atomic hydrogen by electron capture of water molecule from the semiconductor in alkaline solutions.