A method of forming a metal film using a metal carbonyl compound as a material is disclosed that includes the steps of: (a) introducing a reactive gas into a space near a surface of a substrate to be processed; and (b) introducing a gaseous phase material including the metal carbonyl compound into the space on the surface of the substrate to be processed, and depositing the metal film on the surface of the substrate to be processed after step (a). Step (a) is executed in such a manner as to prevent substantial deposition of the metal film on the substrate to be processed.