Atomic-scale smooth Pt electrode films have been deposited on MgO/TiN buffered Si (100) by the pulsed laser deposition (PLD) technique. The whole growth process of the multilayer films was monitored by using in-situ reflection high energy electron diffraction (RHEED) apparatus. The Pt/MgO/TiN/Si(100) stacked structure was also characterized by X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The HREED observations show that the growth mode of the Pt electrode film is 2D layer-by-layer growth. It is found that the (111)-oriented Pt electrode film has a crystallinity comparable to that of monocrystals. The achievement of the quasi-single-crystal Pt electrode film with an atomic-scale smooth surface is ascribed to the improved crystalline quality of the MgO film.