Recent research has highlighted the potential use of "smart" films, such as graphene sheets, that would allow for the controlled release of a variety of therapeutic drugs. Taking full advantage of these versatile conducting sheets, we investigated the novel concept of applying graphene oxide (GO) and reduced graphene oxide (rGO) materials as both barrier and conducting layers that afford controlled entrapment and release of any molecules of interest. We fabricated multilayered nanofilm architectures using a hydrolytically degradable cationic poly(β-amino ester) (PAE), a model protein antigen, ovalbumin (OVA) as a building block along with the GO and rGO. We successfully showed that these multilayer films are capable of blocking the initial burst release of OVA, and they can be triggered to precisely control the release upon the application of electrochemical potential. This new drug delivery platform will find its usefulness in various transdermal drug delivery devices where on-demand control of drug release from the surface is necessary.