Nano-cube MgO particles were formed on Si substrates by deposition of an MgO target using pulsed laser deposition method. An epitaxial film grows on Si(001) substrate with its contraction of lattice constants. In this study, expecting high quality MgO film, the MgO film prepared in the oxygen pressure ranging from 75-400 mTorr at the high temperature of -750 degrees C. The deposited MgO showed the growth of (001) preferred orientation on the Si(001) substrate. However, X-ray Photoelectron Spectroscopy (XPS) indicated the MgO film did not form a continuous film on the Si surface. Interestingly, the surface morphology observed by an Atomic Force Microscopy (AFM) showed nano-cube MgO particles scattered on the smooth surface of Si substrate. After annealing the nano-cube MgO, the shape of MgO particles were changed from nano-cube to round shaped particles. The AFM image of the surface showed round shaped MgO nanoparticles scattered on rough surface. X-ray Diffraction (XRD) revealed the epitaxial growth of MgO(001) with cubic on cubic arrangement on the Si(001) substrate (MgO[100] parallel to Si[100]).