A glycyrrhizin decorated graphene hybrid materials (GL-G) was synthesized, which is a layer-to-layer sandwich construction. The results of characterization indicate that a photo induced electron transfer process or efficient energy transferring along the GL-G interface. Furthermore, the as-made hybrid material was used as a modifier of the glassy carbon electrode to construct a sensor (GL-G/GCE). Using p-nitrophenol as a model compound, the novel sensor demonstrated a highly enhanced electrochemical activity for it. The peak current of p-nitrophenol was significantly improved at the sensor.