ZnO nanostructures were formed on a Si substrate by off-axis pulsed laser deposition(PLD) system in which a substrate plane was tilted toward a plume propagation direction. Atomic force microscopy (AFM) showed islands of 20∼40 nm width. From the x-ray diffraction (XRD) pattern exhibiting only (002) ZnO peak, the islands observed in AFM image were found to well crystallized. Optical bandgap enlargement from 3.26 eV to 3.35 and 3.47 eV due to the quantum size effect of ZnO nanostructures were observed by Photoluminescence (PL) at room temperature.