The fabrication of material with an atomic scale manipulation requires the suitable advanced substrate for epitaxial growth without the effect by the substrate lattice structure. Hexagonal boron nitride (h-BN) can be the advanced substrate for atomic manipulation due to van der Waals' gap with little attractive force along to c axis. We have successfully synthesized h-BN layer on the co-deposited Cu/BN film by surface segregation phenomena using helicon wave plasma enhanced radio frequency (rf) magnetron sputtering system. Auger electron spectroscopy (AES) and X-ray photon spectroscopy (XPS) analysis showed that the h-BN composite segregated on the surface of Cu/BN film covered over 95% of the film annealed at 900 K for 30 min. Atomic forces microscopy (AFM) and scanning tunneling microscopy (STM) analysis showed that attractive force on the film surface is uniformly distributed to an extent of 2nN and that the h-BN surface can be a good electric insulator like sintered h-BN plate,