We have studied the dependence of Schottky junction (I–V) characteristics on the metal contact size in metal–semiconductor (M–S) junctions using different metal nanoprobe sizes. The results show strong dependence of (I–V) characteristics on the nanoprobe size when it is in contact with a semiconductor substrate. The results show the evolution from sub-10 nm reversed Schottky diode behavior to the normal diode behavior at 100 nm. These results also indicate the direct correlation between the electric field at the M–S interface and the Schottky rectification behavior. The effect of the metal contact size on nano-Schottky diode structure is clearly demonstrated, which would help in designing a new type of nano-devices at sub-10 nm scale.