Provided is a method of forming a copper (Cu) wiring in a recess formed to have a predetermined pattern in an insulating film formed on a surface of a substrate. The method includes: forming a barrier film at least on a surface of the recess, the barrier film serving as a barrier for blocking diffusion of Cu; forming a Ru film on the barrier film by Chemical Mechanical Deposition (CVD); forming a Cu alloy film on the Ru film by Physical Vapor Deposition (PVD) to bury the recess; forming a Cu wiring using the Cu alloy film buried in the recess; and forming a dielectric film on the Cu wiring.