Stainless steel (STS) films were annealed in a thermal quartz tube and covered with graphene to improve their anticorrosive properties. Graphene was synthesized via the chemical vapor deposition method and transferred onto the surface of the STS film by the layer-by-layer approach. The structure of the STS film changed from alpha-Fe to gamma-Fe after annealing at 700 C for 1 h, resulting in an increase of 82.72% in the inhibition efficiency. However, one-layer graphene acted as a conductive pathway and therefore deteriorated the anticorrosive properties of the STS film. To overcome this problem, graphene was transferred layer by layer onto the STS film. It was found that transfer of three layers of graphene onto the STS film resulted in a 91.57% increase in the inhibition efficiency. Therefore, thermal annealing and transfer of multilayer graphene are considered to be effective in enhancing the anticorrosive properties of STS films.