A novel sandwich nanomedicine (GO-BNN6) for near-infrared (NIR) light responsive release of nitric oxide (NO) has been constructed by self-assembly of graphene oxide (GO) nanosheets and a NO donor BNN6 through the π-π stacking interaction. The GO-BNN6 nanomedicine has an extraordinarily high drug loading capacity (1.2 mg BNN6 per mg GO), good thermal stability, and high NIR responsiveness. The NO release from GO-BNN6 can be easily triggered and effectively controlled by adjusting the switching, irradiation time and power density of NIR laser. The intracellular NIR-responsive release of NO from the GO-BNN6 nanomedicine causes a remarkable anti-cancer effect.