Nanocrystalline Ni ?lms were grown directly on n-Si(111) substrates without any bu?er layer by using pulsed electrodeposition in a non-aqueous NiCl₂ + methanol solution. The structure of the energy band of the Ni²⁺/n-Si(111) interface in a 0.1-M NiCl₂ electrolyte was investigated by using the cyclic voltammogram (CV) and the Mott-Schottky (MS) relation. The CV results indicated that the Ni²⁺/n-Si(111) interface showed a good diode behavior by forming a Schottky barrier. From the CV and the MS relation, the ?atband potential of the n-Si(111) substrate and the equilibrium redox potential of Ni²⁺ ions were -0.508 V and -0.294 V, respectively. We con?rmed that the average size of the Ni nanoparticles obtained by using pulsed electrodeposition depended on the frequency of the applied potential pulse. When the frequency was varied from 20 Hz to 900 Hz, the average size of the Ni nanoparticles varied in the range from 48 nm to 130 nm. The nucleation and growth kinetics during the initial stages of Ni²⁺/n-Si(111) interface formation, as studied by using current transients, were indicative of an 3-dimensional, instantaneous nucleation, followed by a di?usion-limited growth mode.