A method of forming and processing of graphene is disclosed based on exposure and selective intercalation of the partially graphene-covered metal substrate with atomic or molecular intercalation species such as oxygen (O2) and nitrogen oxide (NO2). The process of intercalation lifts the strong metal-carbon coupling and restores the characteristic Dirac behavior of isolated monolayer graphene. The interface of graphene with metals or metal-decorated substrates also provides for controlled chemical reactions based on novel functionality of the confined space between a metal surface and a graphene sheet.