The electrochemical behaviors of shikonin at a poly(diallyldimethylammonium chloride) functionalized graphene sheets modified glass carbon electrode(PDDA-GS/GCE) have been investigated.Shikonin could exhibit a pair of well-defined redox peaks at the PDDA-GS/GCE located at 0.681 V(Epa) and 0.662 V(Epc)[vs.saturated calomel electrode(SCE)] in 0.1 mol/L phosphate buffer solution(pH=2.0) with a peak-to-peak separation of about 20 mV,revealing a fast electron-transfer process.Moreover, the current response was remarkably increased at PDDA-GS/GCE compared with that at the bare GCE.The electrochemical behaviors of shikonin at the modified electrode were investigated.And the results indicate that the reaction involves the transfer of two electrons, accompanied by two protons and the electrochemical process is a diffusional-contro11ed electrode process.The electrochemical parameters of shikonin at the modified electrode, the electron-transfer coefficient(α), the electron-transfer number(n) and the electrode reaction rate constant(ks) were calculated to be as 0.53, 2.18 and 3.6 s-1, respectively.Under the optimal conditions, the peak current of differential pulse voltammetry(DPV) increased linearly with the shikonin concentration in a range from 9.472× 10-8 mol/L to 3.789× 10-6 mol/L with a detection limit of 3.157× 10-8 mol/L.The linear regression equation was Ip=0.7366c+0.7855(R=0.9978;Ip: 10-7 A, c: 10-8 mol/L).In addition, the modified glass carbon electrode also exhibited good stability, selectivity and acceptable reproducibility that could be used for the sensitive, simple and rapid determination of shikonin in real samples.Therefore, the present work offers a new way to broaden the analytical application of graphene in pharmaceutical analysis.