Hybrid hydrogel membranes composed of reduced graphene oxide (rGO) nanosheets and a poly (vinyl alcohol) (PVA) matrix were investigated as an electrically responsive drug release system. The rGO nanosheets in the matrix act as a physical barrier to inhibit the release of the model anesthetic drug, lidocaine hydrochloride, but the highly responsive release can be enhanced by the presence of rGO when exposed to an electrical stimulus. More interestingly, the on-demand drug release profiles of the assembled rGO-PVA hydrogel into a chip-like device can be highly controlled by an external electrical field. Release profiles ranging from a slow-elution pattern to a rapid release under electrical field treatment can be achieved by manipulating the rGO-PVA composition. Moreover, under cyclic exposure to an electrical stimulus, a highly controllable and repeatedly pulsatile release with desirable precision is obtained from the rGO-PVA hydrogel, implying that the hydrogel exhibits excellent anti-fatigue properties. By combining with the enhanced structural integrity and biocompatibility, the electrically responsive rGO-PVA hydrogel has demonstrated potential biological applications in drug delivery systems. In addition, the easy loading of hydrophilic drugs into the rGO-PVA hydrogel opens up a promising future in biological applications, such as transdermal therapy and wound healing.