Provided are a multi-layered graphene film, a method of manufacturing the multi-layered graphene film, and an energy storage device using the multi-layered graphene film as an electrode. The multi-layered graphene film includes a first graphene layer, a spacer layer provided on the first graphene layer, and an upper graphene layer provided on the spacer layer. The spacer layer is provided to maintain a desired distance between the first graphene layer and the upper graphene layer. A plurality of layers with different layer configurations are further provided between the spacer layer and the upper graphene layer. The spacer layer may a graphene or a graphene oxide layer.