We demonstrate that graphene oxide can be reversibly reduced and oxidized using electrical stimulus. Controlled reduction and oxidation in two-terminal devices containing multilayer graphene oxide films are shown to result in switching between partially reduced graphene oxide and graphene, a process which modifies the electronic and optical properties. High-resolution tunneling current and electrostatic force imaging reveal that graphene oxide islands are formed on multilayer graphene, turning graphene into a self-assembled heterostructure random nanomesh. Charge storage and resistive switching behavior is observed in two-terminal devices made of multilayer graphene oxide films, correlated with electrochromic effects. Tip-induced reduction and oxidation are also demonstrated. Results are discussed in terms of thermodynamics of oxidation and reduction reactions. © 2011 American Chemical Society.